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Sample records for atomic oxygen radical

  1. β-diketones containing oxygen atom in fluorinated radical

    International Nuclear Information System (INIS)

    Shivanyuk, A.F.; Kudryavtseva, L.S.; Lozinskij, M.O.; Neplyuev, V.M.; Fialkov, Yu.A.; Bratolyubova, A.G.

    1981-01-01

    The synthesis of a number of new aliphatic fluorinated β- diketones containing oxygen atom in fluorinated radical of linear or cyclic structure is described. The reaction of combination with aryldiazonium salts resulting in the formation of corresponding arylhydrazones of fluorinated triketones is studied. It is shown that as a result of arylhydrazone condensation with hydroxylamine, hydrazine and its substituted derivatives the fluorine-containing derivatives of isoxazol and pyrazol are formed [ru

  2. beta. -diketones containing oxygen atom in fluorinated radical

    Energy Technology Data Exchange (ETDEWEB)

    Shivanyuk, A.F.; Kudryavtseva, L.S.; Lozinskij, M.O.; Neplyuev, V.M.; Fialkov, Yu.A.; Bratolyubova, A.G. (AN Ukrainskoj SSR, Kiev. Inst. Organicheskoj Khimii)

    1981-10-01

    The synthesis of a number of new aliphatic fluorinated ..beta..-diketones containing oxygen atom in fluorinated radical of linear or cyclic structure is described. The reaction of combination with aryldiazonium salts resulting in the formation of corresponding arylhydrazones of fluorinated triketones is studied. It is shown that as a result of arylhydrazone condensation with hydroxylamine, hydrazine and its substituted derivatives the fluorine-containing derivatives of isoxazol and pyrazol are formed.

  3. Surface modification of polystyrene with atomic oxygen radical anions-dissolved solution

    International Nuclear Information System (INIS)

    Wang Lian; Yan Lifeng; Zhao Peitao; Torimoto, Yoshifumi; Sadakata, Masayoshi; Li Quanxin

    2008-01-01

    A novel approach to surface modification of polystyrene (PS) polymer with atomic oxygen radical anions-dissolved solution (named as O - water) has been investigated. The O - water, generated by bubbling of the O - (atomic oxygen radical anion) flux into the deionized water, was characterized by UV-absorption spectroscopy and electron paramagnetic resonance (EPR) spectroscopy. The O - water treatments caused an obvious increase of the surface hydrophilicity, surface energy, surface roughness and also caused an alteration of the surface chemical composition for PS surfaces, which were indicated by the variety of contact angle and material characterization by atomic force microscope (AFM) imaging, field emission scanning electron microscopy (FESEM), X-ray photoelectron spectroscopy (XPS), and attenuated total-reflection Fourier transform infrared (ATR-FTIR) measurements. Particularly, it was found that some hydrophilic groups such as hydroxyl (OH) and carbonyl (C=O) groups were introduced onto the polystyrene surfaces via the O - water treatment, leading to the increases of surface hydrophilicity and surface energy. The active oxygen species would react with the aromatic ring molecules on the PS surfaces and decompose the aromatic compounds to produce hydrophilic hydroxyl and carbonyl compounds. In addition, the O - water is also considered as a 'clean solution' without adding any toxic chemicals and it is easy to be handled at room temperature. Present method may suit to the surface modification of polymers and other heat-sensitive materials potentially

  4. Migration of methyl and phenyl radicals, oxygen and sulphur atoms in certain diphenylthiophosphorane derivatives under electron impact

    International Nuclear Information System (INIS)

    Cauquis, G.; Divisia, B.; Ulrich, J.

    The fragmentation of various diphenylthiophosphoranes (Ph 2 P(S)R) subjected to electron impact gives rise to rearrangements dependent on the nature of the radical R. Migrations of phenyl or methyl radicals from phosphorus towards sulphur were thus observed for R=Ph, CH 3 , CH 2 Ph and NH 2 . When an electrophilic centre is formed, during a fragmentation, on a carbon in the α-position of the diphenylthiophosphoranyl radical, migrations of sulphur atoms and phenyl radicals take place from the phosphorus towards the carbon. This is found to be the case with certain fragmentations of diazo 5 and 6 compounds [fr

  5. Matrix-isolation studies on the radiation-induced chemistry in H₂O/CO₂ systems: reactions of oxygen atoms and formation of HOCO radical.

    Science.gov (United States)

    Ryazantsev, Sergey V; Feldman, Vladimir I

    2015-03-19

    The radiation-induced transformations occurring upon X-ray irradiation of solid CO2/H2O/Ng systems (Ng = Ar, Kr, Xe) at 8-10 K and subsequent annealing up to 45 K were studied by Fourier transform infrared spectroscopy. The infrared (IR) spectra of deposited matrices revealed the presence of isolated monomers, dimers, and intermolecular H2O···CO2 complexes. Irradiation resulted in effective decomposition of matrix-isolated carbon dioxide and water yielding CO molecules and OH radicals, respectively. Annealing of the irradiated samples led to formation of O3, HO2, and a number of xenon hydrides of HXeY type (in the case of xenon matrices). The formation of these species was used for monitoring of the postirradiation thermally induced chemical reactions involving O and H atoms generated by radiolysis. It was shown that the radiolysis of CO2 in noble-gas matrices produced high yields of stabilized oxygen atoms. In all cases, the temperatures at which O atoms become mobile and react are lower than those of H atoms. Dynamics and reactivity of oxygen atoms was found to be independent of the precursor nature. In addition, the formation of HOCO radicals was observed in all the noble-gas matrices at remarkably low temperatures. The IR spectra of HOCO and DOCO were first characterized in krypton and xenon matrices. It was concluded that the formation of HOCO was mainly due to the radiation-induced evolution of the weakly bound H2O···CO2 complexes. This result indicates the significance of weak intermolecular interactions in the radiation-induced chemical processes in inert low-temperature media.

  6. Oxygen free radicals in rheumatoid arthritis

    NARCIS (Netherlands)

    P. Biemond (Pieter)

    1986-01-01

    textabstractCurrent knowledge strongly suggests that oxygen free radicals are involved in the pathogenesis of RA. Additional information about the mechanism of free radical attack is necessary in order to find out if interaction with the mechanism of free radical damage can be used in the treatment

  7. 248-NM Laser Photolysis of CHBr3/O-Atom Mixtures: Kinetic Evidence for UV CO(A)-Chemiluminescence in the Reaction of Methylidyne Radicals With Atomic Oxygen

    National Research Council Canada - National Science Library

    Vaghjiani, Ghanshyam L

    2005-01-01

    4TH Positive and Cameron band emissions from electronically excited CO have been observed for the first time in 248-nm pulsed laser photolysis of a trace amount of CHBr3 vapor in an excess of O-atoms...

  8. prepared via atom transfer radical polymerization, reverse atom

    Indian Academy of Sciences (India)

    Synthesis and characterization of poly(2-ethylhexyl acrylate) prepared via atom transfer radical polymerization, reverse atom transfer radical polymerization and ... Zydex Industries, 25-A Gandhi Oil Mill Compound, Gorwa, Vadodara 390 016, India; Rubber Technology Centre, Indian Institute of Technology Kharagpur, ...

  9. Kinetics of elementary atom and radical reactions: Progress report

    International Nuclear Information System (INIS)

    Gordon, R.J.

    1986-01-01

    Our research program is concerned with the kinetics of elementary gas phase reactions and energy transfer involving polyatomic molecules. We report here on three ongoing projects: The reaction of oxygen atoms with hydrogen molecules, the electronic relaxation of NH radicals, and the vibrational relaxation of highly excited SF 6 molecules. 10 refs., 5 figs

  10. The Interaction between Graphene and Oxygen Atom

    Directory of Open Access Journals (Sweden)

    Hao Yifan

    2016-01-01

    Full Text Available Based on the density function theory (DFT method, the interaction between the graphene and oxygen atom is simulated by the B3LYP functional with the 6-31G basis set. Due to the symmetry of graphene (C54H18, D6h, a representative patch is put forward to represent the whole graphene to simplify the description. The representative patch on the surface is considered to gain the potential energy surface (PES. By the calculation of the PES, four possible stable isomers of the C54H18-O radical can be obtained. Meanwhile, the structures and energies of the four possible stable isomers, are further investigated thermodynamically, kinetically, and chemically. According to the transition states, the possible reaction mechanism between the graphene and oxygen atom is given.

  11. Radical fragmentation of six-membered oxygen-containing heterocycles

    International Nuclear Information System (INIS)

    Petryaev, E.P.; Kosobutskij, V.S.; Shadyro, O.I.

    1982-01-01

    Using chromatography, the composition and radiation-chemical yields of final products of desctruction of six-member saturated oxygen-containing heterocycles (the effect of #betta#-radiation on aqueous solutions of tetrahydropyran, 1,3-dioxane, 2,2 dimethyl-1,3 dioxane, 1,4-dioxane, paraldehyde) have been determined. It is established that the identified products are formed at the expense of decomposition of primary radicals of the initial compounds and point to the realization of the following fragmentation ways: 1) #betta#-scattering, 2) #betta#-scattering with a subsequent 1,5 migration of an H atom, 3) simultaneous rupture of two vicinal, relative to the radical center, bonds. A formation mechanism of the substances desctruction products is suggested. Material balance of the product yields of 1,3-dioxane radical synchronous decomposition is presented

  12. Electron affinities of atoms, molecules, and radicals

    International Nuclear Information System (INIS)

    Christodoulides, A.A.; McCorkle, D.L.; Christophorou, L.G.

    1982-01-01

    We review briefly but comprehensively the theoretical, semiempirical and experimental methods employed to determine electron affinities (EAs) of atoms, molecules and radicals, and summarize the EA data obtained by these methods. The detailed processes underlying the principles of the experimental methods are discussed very briefly. It is, nonetheless, instructive to recapitulate the definition of EA and those of the related quantities, namely, the vertical detachment energy, VDE, and the vertical attachment energy, VAE. The EA of an atom is defined as the difference in total energy between the ground state of the neutral atom (plus the electron at rest at infinity) and its negative ion. The EA of a molecule is defined as the difference in energy between the neutral molecule plus an electron at rest at infinity and the molecular negative ion when both, the neutral molecules and the negative ion, are in their ground electronic, vibrational and rotational states. The VDE is defined as the minimum energy required to eject the electron from the negative ion (in its ground electronic and nuclear state) without changing the internuclear separation; since the vertical transition may leave the neutral molecule in an excited vibrational/rotational state, the VDE, although the same as the EA for atoms is, in general, different (larger than), from the EA for molecules. Similarly, the VAE is defined as the difference in energy between the neutral molecule in its ground electronic, vibrational and rotational states plus an electron at rest at infinity and the molecular negative ion formed by addition of an electron to the neutral molecule without allowing a change in the intermolecular separation of the constituent nuclei; it is a quantity appropriate to those cases where the lowest negative ion state lies above the ground states of the neutral species and is less or equal to EA

  13. Role of plasma enhanced atomic layer deposition reactor wall conditions on radical and ion substrate fluxes

    Energy Technology Data Exchange (ETDEWEB)

    Sowa, Mark J., E-mail: msowa@ultratech.com [Ultratech/Cambridge NanoTech, 130 Turner Street, Building 2, Waltham, Massachusetts 02453 (United States)

    2014-01-15

    Chamber wall conditions, such as wall temperature and film deposits, have long been known to influence plasma source performance on thin film processing equipment. Plasma physical characteristics depend on conductive/insulating properties of chamber walls. Radical fluxes depend on plasma characteristics as well as wall recombination rates, which can be wall material and temperature dependent. Variations in substrate delivery of plasma generated species (radicals, ions, etc.) impact the resulting etch or deposition process resulting in process drift. Plasma enhanced atomic layer deposition is known to depend strongly on substrate radical flux, but film properties can be influenced by other plasma generated phenomena, such as ion bombardment. In this paper, the chamber wall conditions on a plasma enhanced atomic layer deposition process are investigated. The downstream oxygen radical and ion fluxes from an inductively coupled plasma source are indirectly monitored in temperature controlled (25–190 °C) stainless steel and quartz reactors over a range of oxygen flow rates. Etch rates of a photoresist coated quartz crystal microbalance are used to study the oxygen radical flux dependence on reactor characteristics. Plasma density estimates from Langmuir probe ion saturation current measurements are used to study the ion flux dependence on reactor characteristics. Reactor temperature was not found to impact radical and ion fluxes substantially. Radical and ion fluxes were higher for quartz walls compared to stainless steel walls over all oxygen flow rates considered. The radical flux to ion flux ratio is likely to be a critical parameter for the deposition of consistent film properties. Reactor wall material, gas flow rate/pressure, and distance from the plasma source all impact the radical to ion flux ratio. These results indicate maintaining chamber wall conditions will be important for delivering consistent results from plasma enhanced atomic layer deposition

  14. Kinetics of elementary atom and radical reactions

    International Nuclear Information System (INIS)

    Gordon, R.J.

    1990-06-01

    During the past three years we have been working on four problems in the general area of gas phase kinetics and energy transfer of small molecules. These are: (1) measurements of the fine structure populations of ground state oxygen atoms produced in photodissociation reactions; (2) quenching of the Rydberg B ( 1 Σ + ) state of CO; (3) vibrational relaxation of highly excited molecules; and (4) kinetics of hydrogen molecules. The first two topics, which involve transitions between different electronic states of the parent molecule, are a departure from our previous research interests. In the accompanying renewal proposal we discuss plans to pursue these new topics vigorously during the coming year. The third topic is a continuation of our long interest in the energy dependence of the rates laws governing vibrational-to-translational energy transfer of molecules having large initial amounts of vibrational excitation. The final topic is a continuation of our studies of the reaction of O( 3 P) + H 2 . In this work we measured the rate constant for the reaction O( 3 P) with deuterium and also analyzed spectroscopically different sources of vibrationally excited hydrogen for possible future work. We discuss each of these four studies in the following sections

  15. When hydroquinone meets methoxy radical: Hydrogen abstraction reaction from the viewpoint of interacting quantum atoms.

    Science.gov (United States)

    Petković, Milena; Nakarada, Đura; Etinski, Mihajlo

    2018-05-25

    Interacting Quantum Atoms methodology is used for a detailed analysis of hydrogen abstraction reaction from hydroquinone by methoxy radical. Two pathways are analyzed, which differ in the orientation of the reactants at the corresponding transition states. Although the discrepancy between the two barriers amounts to only 2 kJ/mol, which implies that the two pathways are of comparable probability, the extent of intra-atomic and inter-atomic energy changes differs considerably. We thus demonstrated that Interacting Quantum Atoms procedure can be applied to unravel distinct energy transfer routes in seemingly similar mechanisms. Identification of energy components with the greatest contribution to the variation of the overall energy (intra-atomic and inter-atomic terms that involve hydroquinone's oxygen and the carbon atom covalently bound to it, the transferring hydrogen and methoxy radical's oxygen), is performed using the Relative energy gradient method. Additionally, the Interacting Quantum Fragments approach shed light on the nature of dominant interactions among selected fragments: both Coulomb and exchange-correlation contributions are of comparable importance when considering interactions of the transferring hydrogen atom with all other atoms, whereas the exchange-correlation term dominates interaction between methoxy radical's methyl group and hydroquinone's aromatic ring. This study represents one of the first applications of Interacting Quantum Fragments approach on first order saddle points. © 2018 Wiley Periodicals, Inc. © 2018 Wiley Periodicals, Inc.

  16. TRANSITION METAL CATALYSIS IN CONTROLLED RADICAL POLYMERIZATION: ATOM TRANSFER RADICAL POLYMERIZATION. (R826735)

    Science.gov (United States)

    Novel and diversified macromolecular structures, which include polymers with designed topologies (top), compostions (middle), and functionalities (bottom), can be prepared by atom transfer radical polymerization processes. These polymers can be synthesized from a large variety of...

  17. Atom transfer radical polymerization of styrene under pulsed microwave irradiation

    International Nuclear Information System (INIS)

    Cheng Zhenping; Zhu Xiulin; Zhou Nianchen; Zhu Jian; Zhang Zhengbiao

    2005-01-01

    A homogeneous solution atom transfer radical polymerization (ATRP) and reverse atom transfer radical polymerization (RATRP) of styrene (St) in N,N-dimethylformamide (DMF) were successfully carried out under pulsed microwave irradiation (PMI), using 1-bromo-1-phenylethane (1-PEBr)/CuCl/N,N,N',N'',N''-pentamethyldiethylenetriamine (PMDETA) as an initiating system at 85 deg. C and 2,2'-azo-bis-isobutyrontrile (AIBN)/CuCl 2 /PMDETA as an initiating system at 95 deg. C, respectively. The polymerization rates under PMI were greatly increased in comparison with those under identical conventional heating (CH)

  18. Hot oxygen atoms: Their generation and chemistry

    International Nuclear Information System (INIS)

    Ferrieri, R.A.; Chu, Yung Y.; Wolf, A.P.

    1987-01-01

    Oxygen atoms with energies between 1 and 10 eV have been produced through ion beam sputtering from metal oxide targets. Argon ion beams were used on Ta 2 O 5 and V 2 O 5 . Results show that some control may be exerted over the atom's kinetic energy by changing the target. Reactions of the hot O( 3 P) with cis- and trans-butenes were investigated

  19. Rate constants for the reactions of free radicals with oxygen in solution

    International Nuclear Information System (INIS)

    Maillard, B.; Ingold, K.U.; Scaiano, J.C.

    1983-01-01

    The kinetics of the rections of several free radicals with oxygen have been examined in solution at 300 K using laser flash photolysis techniques. The reactions of resonance-stabilized radicals are only slightly slower than those of nonstabilized radicals: for example, for tert-butyl (in cyclohexane), 4.93 x 10 9 ; benzyl, 2.36 x 10 9 (in cyclohexane); cyclohexadienyl (in benzene), 1.64 x 10 9 M -1 s -1 . The reaction of butyl-tin (n-Bu 3 Sn.) radicals is unusually fast (7.5 x 10 9 M -1 s -1 ), a fact that has been tentatively attributed to a relaxation of spin selection rules due to heavy atom effects. 1 table

  20. Oxygen radical microscopy in living plant tissues

    DEFF Research Database (Denmark)

    Kristiansen, Kim Anker; Møller, Ian Max; Schulz, Alexander

    the ROS production stems from the mitochondria and peroxisomes as is seen in animal cells. At the Bioimaging Center at KVL we employ different techniques to induce, detect and monitor ROS production, distribution and in and among living plant cells. Both confocal laser scanning microscopy and 2-photon......Reactive oxygen species (ROS) play a crucial role in a wide variety of processes. Initiation of many different cellular pathways, crosstalk between cells, developmental signalling in planta, programmed cell death and hypersensitive response in connection with plant-pathogen interactions are among...... the different roles ROS play. On the other hand ROS also cause damage to cellular components at sub-lethal to lethal levels. In photosynthesizing plants the major production of ROS origin from the chloroplast. ROS is a by product from the Photosystem I/II handling of light energy. In nonphotosynthesizing plants...

  1. MISSE PEACE Polymers Atomic Oxygen Erosion Results

    Science.gov (United States)

    deGroh, Kim, K.; Banks, Bruce A.; McCarthy, Catherine E.; Rucker, Rochelle N.; Roberts, Lily M.; Berger, Lauren A.

    2006-01-01

    Forty-one different polymer samples, collectively called the Polymer Erosion and Contamination Experiment (PEACE) Polymers, have been exposed to the low Earth orbit (LEO) environment on the exterior of the International Space Station (ISS) for nearly 4 years as part of Materials International Space Station Experiment 2 (MISSE 2). The objective of the PEACE Polymers experiment was to determine the atomic oxygen erosion yield of a wide variety of polymeric materials after long term exposure to the space environment. The polymers range from those commonly used for spacecraft applications, such as Teflon (DuPont) FEP, to more recently developed polymers, such as high temperature polyimide PMR (polymerization of monomer reactants). Additional polymers were included to explore erosion yield dependence upon chemical composition. The MISSE PEACE Polymers experiment was flown in MISSE Passive Experiment Carrier 2 (PEC 2), tray 1, on the exterior of the ISS Quest Airlock and was exposed to atomic oxygen along with solar and charged particle radiation. MISSE 2 was successfully retrieved during a space walk on July 30, 2005, during Discovery s STS-114 Return to Flight mission. Details on the specific polymers flown, flight sample fabrication, pre-flight and post-flight characterization techniques, and atomic oxygen fluence calculations are discussed along with a summary of the atomic oxygen erosion yield results. The MISSE 2 PEACE Polymers experiment is unique because it has the widest variety of polymers flown in LEO for a long duration and provides extremely valuable erosion yield data for spacecraft design purposes.

  2. Monomode microwave-assisted atom transfer radical polymerization

    NARCIS (Netherlands)

    Zhang, H.; Schubert, U.S.

    2004-01-01

    The first monomode microwave-assisted atom transfer radical polymerization (ATRP) is reported. The ATRP of methyl methacrylate was successfully performed with microwave heating, which was well controlled and provided almost the same results as experiments with conventional heating, demonstrating the

  3. Atom transfer radical copolymerization of styrene and butyl acrylate

    NARCIS (Netherlands)

    Chambard, G.; Klumperman, B.; Matyjaszewski, K.

    2000-01-01

    Atom transfer radical polymerization of styrene and butyl acrylate has been investigated from a kinetic point of view. Attention is focused on the activation of the dormant species as well as on the termination that plays a role in these reactions. It has been shown that the activation of a styrene

  4. Fluorophore-based sensor for oxygen radicals in processing plasmas

    International Nuclear Information System (INIS)

    Choudhury, Faraz A.; Shohet, J. Leon; Sabat, Grzegorz; Sussman, Michael R.; Nishi, Yoshio

    2015-01-01

    A high concentration of radicals is present in many processing plasmas, which affects the processing conditions and the properties of materials exposed to the plasma. Determining the types and concentrations of free radicals present in the plasma is critical in order to determine their effects on the materials being processed. Current methods for detecting free radicals in a plasma require multiple expensive and bulky instruments, complex setups, and often, modifications to the plasma reactor. This work presents a simple technique that detects reactive-oxygen radicals incident on a surface from a plasma. The measurements are made using a fluorophore dye that is commonly used in biological and cellular systems for assay labeling in liquids. Using fluorometric analysis, it was found that the fluorophore reacts with oxygen radicals incident from the plasma, which is indicated by degradation of its fluorescence. As plasma power was increased, the quenching of the fluorescence significantly increased. Both immobilized and nonimmobilized fluorophore dyes were used and the results indicate that both states function effectively under vacuum conditions. The reaction mechanism is very similar to that of the liquid dye

  5. Fluorophore-based sensor for oxygen radicals in processing plasmas

    Energy Technology Data Exchange (ETDEWEB)

    Choudhury, Faraz A.; Shohet, J. Leon, E-mail: shohet@engr.wisc.edu [Plasma Processing and Technology Laboratory and Department of Electrical and Computer Engineering, University of Wisconsin-Madison, Madison, Wisconsin 53706 (United States); Sabat, Grzegorz; Sussman, Michael R. [Department of Biochemistry, University of Wisconsin-Madison, Madison, Wisconsin 53706 (United States); Nishi, Yoshio [Department of Electrical Engineering, Stanford University, Stanford, California 94305 (United States)

    2015-11-15

    A high concentration of radicals is present in many processing plasmas, which affects the processing conditions and the properties of materials exposed to the plasma. Determining the types and concentrations of free radicals present in the plasma is critical in order to determine their effects on the materials being processed. Current methods for detecting free radicals in a plasma require multiple expensive and bulky instruments, complex setups, and often, modifications to the plasma reactor. This work presents a simple technique that detects reactive-oxygen radicals incident on a surface from a plasma. The measurements are made using a fluorophore dye that is commonly used in biological and cellular systems for assay labeling in liquids. Using fluorometric analysis, it was found that the fluorophore reacts with oxygen radicals incident from the plasma, which is indicated by degradation of its fluorescence. As plasma power was increased, the quenching of the fluorescence significantly increased. Both immobilized and nonimmobilized fluorophore dyes were used and the results indicate that both states function effectively under vacuum conditions. The reaction mechanism is very similar to that of the liquid dye.

  6. Absolute photoionization cross sections of atomic oxygen

    Science.gov (United States)

    Samson, J. A. R.; Pareek, P. N.

    1985-01-01

    The absolute values of photoionization cross sections of atomic oxygen were measured from the ionization threshold to 120 A. An auto-ionizing resonance belonging to the 2S2P4(4P)3P(3Do, 3So) transition was observed at 479.43 A and another line at 389.97 A. The experimental data is in excellent agreement with rigorous close-coupling calculations that include electron correlations in both the initial and final states.

  7. Measuring oxidation processes: Atomic oxygen flux monitor

    International Nuclear Information System (INIS)

    Anon.

    1991-01-01

    Of the existing 95 high-energy accelerators in the world, the Stanford Linear Collider (SLC) at the Stanford Linear Accelerator Center (SLAC) is the only one of the linear-collider type, where electrons and positrons are smashed together at energies of 50 GeV using linear beams instead of beam rings for achieving interactions. Use of a collider eliminates energy losses in the form of x-rays due to the curved trajectory of the rings, a phenomena known as bremsstrauhlung. Because these losses are eliminated, higher interaction energies are reached. Consequently the SLC produced the first Z particle in quantities large enough to allow measurement of its physical properties with some accuracy. SLAC intends to probe still deeper into the structure of matter by next polarizing the electrons in the beam. The surface of the source for these polarized particles, typically gallium arsenide, must be kept clean of contaminants. One method for accomplishing this task requires the oxidation of the surface, from which the oxidized contaminants are later boiled off. The technique requires careful measurement of the oxidation process. SLAC researchers have developed a technique for measuring the atomic oxygen flux in this process. The method uses a silver film on a quartz-crystal, deposition-rate monitor. Measuring the initial oxidation rate of the silver, which is proportional to the atomic oxygen flux, determines a lower limit on that flux in the range of 10 13 to 10 17 atoms per square centimeter per second. Furthermore, the deposition is reversible by exposing the sensor to atomic hydrogen. This technique has wider applications to processes in solid-state and surface physics as well as surface chemistry. In semiconductor manufacturing where a precise thickness of oxide must be deposited, this technique could be used to monitor the critical flux of atomic oxygen in the process

  8. Working group written presentation: Atomic oxygen

    International Nuclear Information System (INIS)

    Leger, L.J.; Visentine, J.T.

    1989-01-01

    Earlier Shuttle flight experiments have shown NASA and SDIO spacecraft designed for operation in low-Earth orbit (LEO) must take into consideration the highly oxidative characteristics of the ambient flight environment. Materials most adversely affected by atomic oxygen interactions include organic films, advanced (carbon-based) composites, thermal control coatings, organic-based paints, optical coatings, and thermal control blankets commonly used in spacecraft applications. Earlier results of NASA flight experiments have shown prolonged exposure of sensitive spacecraft materials to the LEO environment will result in degraded systems performance or, more importantly, lead to requirements for excessive on-orbit maintenance, with both conditions contributing significantly to increased mission costs and reduced mission objectives. Flight data obtained from previous Space Shuttle missions and results of the Solar Max recovery mission are limited in terms of atomic oxygen exposure and accuracy of fluence estimates. The results of laboratory studies to investigate the long-term (15 to 30 yrs) effects of AO exposure on spacecraft surfaces are only recently available, and qualitative correlations of laboratory results with flight results have been obtained for only a limited number of materials. The working group recommended the most promising ground-based laboratories now under development be made operational as soon as possible to study the full-life effects of atomic oxygen exposure on spacecraft systems

  9. Living atom transfer radical polymerization of 4-acetoxystyrene

    DEFF Research Database (Denmark)

    Gao, Bo; Chen, Xianyi; Ivan, Bela

    1997-01-01

    Living atom transfer radical polymerization (ATRP) of 4-acetoxystyrene (1), a protected 4-vinylphenol, leading to poly(4-acetoxystyrene) with well-defined molecular weight and narrow molecular weight distribution was carried out in bulk with a,a'-dibromoxylene(2)/CuBr/2,2-bipyridine(bpy) as initi......Living atom transfer radical polymerization (ATRP) of 4-acetoxystyrene (1), a protected 4-vinylphenol, leading to poly(4-acetoxystyrene) with well-defined molecular weight and narrow molecular weight distribution was carried out in bulk with a,a'-dibromoxylene(2)/CuBr/2,2-bipyridine......(bpy) as initiating system. A linear (M) over bar(n), versus monomer conversion plot was found in good accordance with the theoretical line, indicating 100% initiating efficiency. The polymerization is first order in respect to monomer up to about 70% monomer conversion. Deviations from linearity at higher conversion...

  10. Two-photon laser-induced fluorescence studies of HS radicals, DS radicals, and I atoms

    Energy Technology Data Exchange (ETDEWEB)

    Tiee, J J; Ferris, M J; Loge, G W; Wampler, F B

    1983-04-15

    A two-photon laser-induced excitation and fluorescence technique has been used to study the A /sup 2/..sigma../sup +/ - X/sup 2/PI transition of HS and DS radicals and various high-lying /sup 4/P/sup 0/, /sup 2/D/sup 0/, and /sup 4/D/sup 0/ states of the I atom. The two-photon excitation cross sections and detection sensitivity are discussed. 13 references, 5 figures.

  11. Non-penetrating states of atomic oxygen

    International Nuclear Information System (INIS)

    Chang, E.S.; Barowy, W.M.; Sakai, H.

    1988-01-01

    Atomic Rydberg transitions have been observed in the 1-5 μm emission spectrum of an oxygen discharge. Proper analysis of these lines requires reinterpretation of previous 3d-nf measurements by explicit inclusion of the theoretical F-level fine structure in the experimental line profiles. The revised triplet-quintet differences in the nF levels are now seen to vary smoothly with n, analogous to the polarization energy in an Edlen plot. The new levels, 5g, 6g, 7g, and 7h also form a straight line according to the polarization formula, thereby confirming the ionization limit to a higher accuracy. (orig.)

  12. Palladium-Catalyzed Atom-Transfer Radical Cyclization at Remote Unactivated C(sp3 )-H Sites: Hydrogen-Atom Transfer of Hybrid Vinyl Palladium Radical Intermediates.

    Science.gov (United States)

    Ratushnyy, Maxim; Parasram, Marvin; Wang, Yang; Gevorgyan, Vladimir

    2018-03-01

    A novel mild, visible-light-induced palladium-catalyzed hydrogen atom translocation/atom-transfer radical cyclization (HAT/ATRC) cascade has been developed. This protocol involves a 1,5-HAT process of previously unknown hybrid vinyl palladium radical intermediates, thus leading to iodomethyl carbo- and heterocyclic structures. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Enhancement by platelets of oxygen radical responses of human neutrophils

    Energy Technology Data Exchange (ETDEWEB)

    McCulloch, K.K.; Powell, J.; Johnson, K.J.; Ward, P.A.

    1986-03-01

    When human blood neutrophils were incubated with immune complexes (consisting of IgG antibody) in the presence of platelets, there was a 2 to 10 fold enhancement in the generation of O-/sub 2/ and H/sub 2/O/sub 2/. This enhancement phenomenon was proportional to the dose of immune complex added and the number of platelets present. The response was not agonist specific since similar enhancement also occurred with the following agonists: phorbol myristate acetate, opsonized zymosan particles and the chemotactic peptide N-formyl-met-leu-phe. The platelet related phenomenon of enhanced O-/sub 2/ generation could not be reproduced by the addition of serotonin, histamine or platelet-derived growth factor and was not affected by prior treatment of platelets with cyclooxygenase inhibitors (indomethacin, piroxicam) or lipoxygenase inhibitors (nafazatrom, BW755C or nordihydroguaiaretic acid). However, activation of platelets by thrombin caused release into the platelet supernatant fluid of a factor that, only in the presence of immune complexes, caused enhanced O-/sub 2/ responses to neutrophils. These data indicate that platelets potentiate oxygen radical responses of human neutrophils and suggest a mechanisms by which platelets may participate in tissue injury which is mediated by oxygen radical products from activated neutrophils.

  14. Enhancement by platelets of oxygen radical responses of human neutrophils

    International Nuclear Information System (INIS)

    McCulloch, K.K.; Powell, J.; Johnson, K.J.; Ward, P.A.

    1986-01-01

    When human blood neutrophils were incubated with immune complexes (consisting of IgG antibody) in the presence of platelets, there was a 2 to 10 fold enhancement in the generation of O- 2 and H 2 O 2 . This enhancement phenomenon was proportional to the dose of immune complex added and the number of platelets present. The response was not agonist specific since similar enhancement also occurred with the following agonists: phorbol myristate acetate, opsonized zymosan particles and the chemotactic peptide N-formyl-met-leu-phe. The platelet related phenomenon of enhanced O- 2 generation could not be reproduced by the addition of serotonin, histamine or platelet-derived growth factor and was not affected by prior treatment of platelets with cyclooxygenase inhibitors (indomethacin, piroxicam) or lipoxygenase inhibitors (nafazatrom, BW755C or nordihydroguaiaretic acid). However, activation of platelets by thrombin caused release into the platelet supernatant fluid of a factor that, only in the presence of immune complexes, caused enhanced O- 2 responses to neutrophils. These data indicate that platelets potentiate oxygen radical responses of human neutrophils and suggest a mechanisms by which platelets may participate in tissue injury which is mediated by oxygen radical products from activated neutrophils

  15. Oxidation of ruthenium thin films using atomic oxygen

    Energy Technology Data Exchange (ETDEWEB)

    McCoy, A.P.; Bogan, J.; Brady, A.; Hughes, G.

    2015-12-31

    In this study, the use of atomic oxygen to oxidise ruthenium thin films is assessed. Atomic layer deposited (ALD) ruthenium thin films (~ 3 nm) were exposed to varying amounts of atomic oxygen and the results were compared to the impact of exposures to molecular oxygen. X-ray photoelectron spectroscopy studies reveal substantial oxidation of metallic ruthenium films to RuO{sub 2} at exposures as low as ~ 10{sup 2} L at 575 K when atomic oxygen was used. Higher exposures of molecular oxygen resulted in no metal oxidation highlighting the benefits of using atomic oxygen to form RuO{sub 2}. Additionally, the partial oxidation of these ruthenium films occurred at temperatures as low as 293 K (room temperature) in an atomic oxygen environment. - Highlights: • X-ray photoelectron spectroscopy study of the oxidation of Ru thin films • Oxidation of Ru thin films using atomic oxygen • Comparison between atomic oxygen and molecular oxygen treatments on Ru thin films • Fully oxidised RuO{sub 2} thin films formed with low exposures to atomic oxygen.

  16. Detection methods for atoms and radicals in the gas phase

    Science.gov (United States)

    Hack, W.

    This report lists atoms and free radicals in the gas phase which are of interest for environmental and flame chemistry and have been detected directly. The detection methods which have been used are discussed with respect to their range of application, specificity and sensitivity. In table 1, detection methods for the five atoms of group IV (C, Si, Ge, Sn, Pb) and about 60 radicals containing at least one atom of group IV are summarized (CH, Cd, Cf, CC1, CBr, Cn, Cs, CSe, CH2, CD2, Chf, Cdf, CHC1, CHBr, CF2, CC12, CBr2, CFC1, CFBr, CH3, CD3, CF3, CH2F, CH2C1, CH2Br, CHF2, CHC12, CHBr2, Hco, Fco, CH30, CD30, CH2OH, CH3S, Nco, CH4N, CH302, CF302; C2, C2N, C2H, C20, C2HO, C2H3, C2F3, C2H5, C2HsO, C2H4OH, CH3CO, CD3CO, C2H3O, C2H502, CH3COO2, C2H4N, C2H6N, C3; Si, SiF, SiF2, SiO, SiC, Si2; Ge, GeC, GeO, GeF, GeF2, GeCl2, Sn, SnF, SnO, SnF2, Pb, PbF, PbF2, PbO, PbS). In table 2 detection methods for about 25 other atoms and 60 radicals are listed: (H, D, O, O2, Oh, Od, HO2, DO2, F, Ci, Br, I, Fo, Cio, BrO, Io, FO2, C1O2, Li, Na, K, Rb, Cs, N, N3, Nh, Nd, Nf, Nci, NBr, NH2, ND2, Nhd, Nhf, NF2, NC12, N2H3, No, NO2, NO3, Hno, Dno, P, Ph, Pd, Pf, Pci, PH2, PD2, PF2, Po, As, AsO, AsS, Sb, Bi, S, S2, Sh, Sd, Sf, SF2, So, Hso, Dso, Sn, Se, Te, Se2, SeH, SeD, SeF, SeO, SeS, SeN, TeH, TeO, Bh, BH2, Bo, Bn, B02, Cd, Hg, UF5). The tables also cite some recent kinetic applications of the various methods.

  17. The pentafluorostyrene endeavours with atom transfer radical polymerization - quo vadis?

    DEFF Research Database (Denmark)

    Hvilsted, Søren

    2014-01-01

    The versatility of the atom transfer radical polymerization (ATRP) of pentafluorostyrene (FS) is comprehensively evaluated. The ATRP of a wide range of monomers derived from FS is likewise discussed with emphasis on the potential polymer applications. A large number of block and star copolymers...... centred around polypentafluorostyrene (PFS) and prepared primarily using the bromomacroinitiator concept is surveyed. Here the main emphasis is on the feasibility of the polymer design, but also the very many different applications are highlighted. The potential grafting onto PFS and PFS block copolymers...... by exploitation of the very labile para-fluorine demonstrates new material architecture possibilities through very mild reaction conditions. Finally the utility of PFS in various conducting materials is elaborated. The amphiphilic nature of PFS in triblock copolymers with polyethers has been exploited for Li+ ion...

  18. Effect of Inhibitors on Atom Transfer Radical Polymerization of MMA

    Institute of Scientific and Technical Information of China (English)

    张鸿; 徐冬梅; 张可达

    2005-01-01

    Effect of a series of inhibitors as additives on atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) with FeCl2/PPh3 as catalyst system was studied, including 2,4,6-trinitrophenol (TNP), 4-methoxyphenol (4-MP), hydroquinone (HQ) and nitrobenzene (NB). It was found that TNP was the only. efficient additive for ATRP among these inhibitors. In the presence of small amounts of TNP, the polymerization proceeded rapidly after induction period to yield the polymers with controlled molecular weights and narrow molecular weight distributions (MWD). The initiating efficiency of the modified catalyst system with TNP was increased. The mechanism was proposed and confirmed by the end group analysis of the polymer.

  19. Functionalization of lanthanum hydroxide nanowires by atom transfer radical polymerization

    International Nuclear Information System (INIS)

    Zhou Mi; Yuan Jinying; Yuan Weizhong; Yin Yingwu; Hong Xiaoyin

    2007-01-01

    Atom transfer radical polymerization (ATRP) has been used to prepare a core-shell hybrid nanostructure successfully: a hard core of single-crystalline lanthanum hydroxide nanowires and a soft shell of polystyrene (PS) brushes. Transmission electron microscopy (TEM) images indicated that the resulting products presented special structures and different thicknesses of polymer layers. The chemical components and grafted PS quantities of the samples were measured by Fourier transform infrared (FT-IR) spectroscopy and thermogravimetric analysis (TGA). The polymers showed narrow polydispersity, which proved that the lanthanum hydroxide nanowires initiated the 'living'/controlled polymerization of styrene. With the modifiability of lanthanum hydroxide nanowires, the solubility increased, which affords a new way to functionalize nanowires

  20. Inactivation of Bacillus atrophaeus and of Aspergillus niger using beams of argon ions, of oxygen molecules and of oxygen atoms

    Energy Technology Data Exchange (ETDEWEB)

    Raballand, V; Benedikt, J; Keudell, A von [Research Group Reactive Plasmas, Ruhr-Universitaet Bochum, 44780 Bochum (Germany); Wunderlich, J [Fraunhofer Institut for Process Engineering and Packaging, Giggenhauser Strasse 35, 85354 Freising (Germany)], E-mail: Achim.vonKeudell@rub.de

    2008-06-07

    The inactivation of spores of Bacillus atrophaeus and of Aspergillus niger using beams of argon ions, of oxygen molecules and of oxygen atoms is studied. Thereby, the conditions occurring in oxygen containing low pressure plasmas are mimicked and fundamental inactivation mechanisms can be revealed. It is shown that the impact of O atoms has no effect on the viability of the spores and that no etching of the spore coat occurs up to an O atom fluence of 3.5 x 10{sup 19} cm{sup -2}. The impact of argon ions with an energy of 200 eV does not cause significant erosion for fluences up to 1.15 x 10{sup 18} cm{sup -2}. However, the combined impact of argon ions and oxygen molecules or atoms causes significant etching of the spores and significant inactivation. This is explained by the process of chemical sputtering, where an ion-induced defect at the surface of the spore reacts with either the incident bi-radical O{sub 2} or with an incident O atom. This leads to the formation of CO, CO{sub 2} and H{sub 2}O and thus to erosion.

  1. Behaviour of oxygen atoms near the surface of nanostructured Nb2O5

    International Nuclear Information System (INIS)

    Cvelbar, U; Mozetic, M

    2007-01-01

    Recombination of neutral oxygen atoms on oxidized niobium foil was studied. Three sets of samples have been prepared: a set of niobium foils with a film of polycrystalline niobium oxide with a thickness of 40 nm, another one with a film thickness of about 2 μm and a set of foils covered with dense bundles of single-crystal Nb 2 O 3 nanowires. All the samples were prepared by oxidation of a pure niobium foil. The samples with a thin oxide film were prepared by exposure of as-received foils to a flux of O-atoms, the samples with a thick polycrystalline niobium oxide were prepared by baking the foils in air at a temperature of 800 deg. C, while the samples covered with nanowires were prepared by oxidation in a highly reactive oxygen plasma. The samples were exposed to neutral oxygen atoms from a remote oxygen plasma source. Depending on discharge parameters, the O-atom density in the postglow chamber, as measured with a catalytic probe, was between 5 x 10 20 and 8 x 10 21 m -3 . The O-atom density in the chamber without the samples was found rather independent of the probe position. The presence of the samples caused a decrease in the O-atom density. Depending on the distance from the samples, the O-atom density was decreased up to 5 times. The O-atom density also depended on the surface morphology of the samples. The strongest decrease in the O-atom density was observed with the samples covered with dense bundles of nanowires. The results clearly showed that niobium oxide nanowires exhibit excellent catalytic behaviour for neutral radicals and can be used as catalysts of exhaust radicals found in many applications

  2. Oxygen free radical altered immunoglobin G in the etiopathogenesis of rheumatoid arthritis

    NARCIS (Netherlands)

    H.A. Kleinveld (Henk)

    1990-01-01

    textabstractThe particular association of RA with anti-lgG antibodies suggests an important role of lgG in the etiology and pathology of RA. One of the suggested mechanisms by which lgG could be altered is exposure to oxygen free radicals. During inflammation large amounts of oxygen free radicals

  3. DPPH and oxygen free radicals as pro-oxidant of biomolecules.

    Science.gov (United States)

    Letelier, María Eugenia; Molina-Berríos, Alfredo; Cortés-Troncoso, Juan; Jara-Sandoval, José; Holst, Marianne; Palma, Karina; Montoya, Margarita; Miranda, Dante; González-Lira, Víctor

    2008-03-01

    Numerous investigations exist about the alterations that oxygen free radicals can provoke on biomolecules; these modifications can be prevented and/or reversed by different antioxidants agents. On the other hand, 2,2-diphenyl-1-picrylhydrazyl radical (DPPH), a stable nitrogen synthetic radical, is used to evaluate the antioxidant capacity of medicinal herbal products; however, the structural changes that this radical provoke on the herbal active principles are not clear yet. In this work, we compared the redox reactivity of oxygen free radicals and DPPH radical on phospholipids and protein thiol groups present in rat liver microsomes. Cu2+/ascorbate was used as generator system of oxygen free radical and as antioxidant, an extract of Buddleja globosa's leaves. Cu2+/ascorbate provoked microsomal lipid peroxidation, microsomal thiols oxidation and oxygen consumption; all of these phenomena were inhibited by B. globosa extract. On the other hand, DPPH was bleached in different extension by the herbal extract and phosphatidyl choline; beside, DPPH decreased microsomal thiols content, but this phenomenon were not prevented by the herbal extract. Furthermore, DPPH did not induce oxygen consumption and neither modified the oxygen consumption induced by Cu2+/ascorbate. Distinct redox mechanisms may explain the differences between the reactivity of DPPH and oxygen free radicals on biomolecules, which is discussed.

  4. Boron nitride nanosheets as oxygen-atom corrosion protective coatings

    International Nuclear Information System (INIS)

    Yi, Min; Shen, Zhigang; Zhao, Xiaohu; Liang, Shuaishuai; Liu, Lei

    2014-01-01

    The research of two-dimensional nanomaterials for anticorrosion applications is just recently burgeoning. Herein, we demonstrate the boron nitride nanosheets (BNNSs) coatings for protecting polymer from oxygen-atom corrosion. High-quality BNNSs, which are produced by an effective fluid dynamics method with multiple exfoliation mechanisms, can be assembled into coatings with controlled thickness by vacuum filtration. After exposed in atom oxygen, the naked polymer is severely corroded with remarkable mass loss, while the BNNSs-coated polymer remains intact. Barrier and bonding effects of the BNNSs are responsible for the coating's protective performance. These preliminary yet reproducible results pave a way for resisting oxygen-atom corrosion

  5. Formation and properties of metal-oxygen atomic chains

    DEFF Research Database (Denmark)

    Thijssen, W.H.A.; Strange, Mikkel; de Brugh, J.M.J.A.

    2008-01-01

    of longer atomic chains. The mechanical and electrical properties of these diatomic chains have been investigated by determining local vibration modes of the chain and by measuring the dependence of the average chain-conductance on the length of the chain. Additionally, we have performed calculations......Suspended chains consisting of single noble metal and oxygen atoms have been formed. We provide evidence that oxygen can react with and be incorporated into metallic one-dimensional atomic chains. Oxygen incorporation reinforces the linear bonds in the chain, which facilitates the creation...

  6. With medium-chain triglycerides, higher and faster oxygen radical production by stimulated polymorphonuclear leukocytes occurs.

    Science.gov (United States)

    Kruimel, J W; Naber, A H; Curfs, J H; Wenker, M A; Jansen, J B

    2000-01-01

    Parenteral lipid emulsions are suspected of suppressing the immune function. However, study results are contradictory and mainly concern the conventional long-chain triglyceride emulsions. Polymorphonuclear leukocytes were preincubated with parenteral lipid emulsions. The influence of the lipid emulsions on the production of oxygen radicals by these stimulated leukocytes was studied by measuring chemiluminescence. Three different parenteral lipid emulsions were tested: long-chain triglycerides, a physical mixture of medium- and long-chain triglycerides, and structured triglycerides. Structured triglycerides consist of triglycerides where the medium- and long-chain fatty acids are attached to the same glycerol molecule. Stimulated polymorphonuclear leukocytes preincubated with the physical mixture of medium- and long-chain triglycerides showed higher levels of oxygen radicals (p triglycerides or structured triglycerides. Additional studies indicated that differences in results of various lipid emulsions were not caused by differences in emulsifier. The overall production of oxygen radicals was significantly lower after preincubation with the three lipid emulsions compared with controls without lipid emulsion. A physical mixture of medium- and long-chain triglycerides induced faster production of oxygen radicals, resulting in higher levels of oxygen radicals, compared with long-chain triglycerides or structured triglycerides. This can be detrimental in cases where oxygen radicals play either a pathogenic role or a beneficial one, such as when rapid phagocytosis and killing of bacteria is needed. The observed lower production of oxygen radicals by polymorphonuclear leukocytes in the presence of parenteral lipid emulsions may result in immunosuppression by these lipids.

  7. Antioxidant capacity and oxygen radical diseases in the preterm newborn.

    Science.gov (United States)

    Rogers, S; Witz, G; Anwar, M; Hiatt, M; Hegyi, T

    2000-06-01

    Bronchopulmonary dysplasia, intraventricular hemorrhage, necrotizing enterocolitis, and retinopathy of prematurity may be different manifestations of oxygen radical diseases of prematurity (ORDP). To test the hypothesis that the antioxidant capacity of cord blood serum will predict risk of ORDP. An inception cohort of premature neonates was followed up from birth until discharge or death to determine if outcome was related to cord blood serum antioxidant capacity, as determined by a manual assay measuring the relative inhibition of oxidation of 2,2'-azino-di-(3-ethylbenzthiazoline)-6 sulfonic acid (ABTS). Possible correlations between antioxidant capacity and various perinatal factors were also tested. Level 3 newborn intensive care unit. All inborn very low-birth-weight neonates from whom cord blood was available and for whom maternal consent was obtained were included. Newborns who died in the first week of life or who had major congenital malformations were excluded. A convenience sample of newborns weighing more than 1500 g was used to perfect assay and explore confounders. Significant ORDP was defined as the presence of intraventricular hemorrhage greater than grade 2, retinopathy of prematurity greater than stage 1, bronchopulmonary dysplasia at the postconceptional age of 36 weeks, or necrotizing enterocolitis with the hypothesis that neonates with ORDP will have lower antioxidant capacity in cord blood serum. Serum antioxidant capacity at birth correlated with gestational age for the entire sample of 41 neonates and for the 26 neonates born before 32 weeks' gestation. After correction for gestational age, cord serum antioxidant capacity did not correlate with maternal smoking, preeclampsia, chorioamnionitis, cord pH Apgar scores, or any of the ORDP studied. Cord serum antioxidant capacity correlates with gestational age but does not predict ORDP risk.

  8. Reactivity of amino acid anions with nitrogen and oxygen atoms.

    Science.gov (United States)

    Wang, Zhe-Chen; Li, Ya-Ke; He, Sheng-Gui; Bierbaum, Veronica M

    2018-02-14

    For many decades, astronomers have searched for biological molecules, including amino acids, in the interstellar medium; this endeavor is important for investigating the hypothesis of the origin of life from space. The space environment is complex and atomic species, such as nitrogen and oxygen atoms, are widely distributed. In this work, the reactions of eight typical deprotonated amino acids (glycine, alanine, cysteine, proline, aspartic acid, histidine, tyrosine, and tryptophan) with ground state nitrogen and oxygen atoms are studied by experiment and theory. These amino acid anions do not react with nitrogen atoms. However, the reactions of these ions with oxygen atoms show an intriguing variety of ionic products and the reaction rate constants are of the order of 10 -10 cm 3 s -1 . Density functional calculations provide detailed mechanisms of the reactions, and demonstrate that spin conversion is essential for some processes. Our study provides important data and insights for understanding the kinetic and dynamic behavior of amino acids in space environments.

  9. Rate constant for the reaction of atomic oxygen with phosphine at 298 K

    Science.gov (United States)

    Stief, L. J.; Payne, W. A.; Nava, D. F.

    1987-01-01

    The rate constant for the reaction of atomic oxygen with phosphine has been measured at 298 K using flash photolysis combined with time-resolved detection of O(3P) via resonance fluorescence. Atomic oxygen was produced by flash photolysis of N2O or NO highly diluted in argon. The results were shown to be independent of (PH3), (O), total pressure and the source of O(3P). The mean value of all the experiments is k1 = (3.6 + or -0.8) x 10 to the -11th cu cm/s (1 sigma). Two previous measurements of k1 differed by more than an order of magnitude, and the results support the higher value obtained in a discharge flow-mass spectrometry study. A comparison with rate data for other atomic and free radical reactions with phosphine is presented, and the role of these reactions in the aeronomy or photochemistry of Jupiter and Saturn is briefly considered.

  10. Singlet Oxygen and Free Radical Reactions of Retinoids and Carotenoids—A Review

    Science.gov (United States)

    Truscott, T. George

    2018-01-01

    We report on studies of reactions of singlet oxygen with carotenoids and retinoids and a range of free radical studies on carotenoids and retinoids with emphasis on recent work, dietary carotenoids and the role of oxygen in biological processes. Many previous reviews are cited and updated together with new data not previously reviewed. The review does not deal with computational studies but the emphasis is on laboratory-based results. We contrast the ease of study of both singlet oxygen and polyene radical cations compared to neutral radicals. Of particular interest is the switch from anti- to pro-oxidant behavior of a carotenoid with change of oxygen concentration: results for lycopene in a cellular model system show total protection of the human cells studied at zero oxygen concentration, but zero protection at 100% oxygen concentration. PMID:29301252

  11. Tailoring of materials by atomic oxygen from ECR plasma source

    International Nuclear Information System (INIS)

    Naddaf, Munzer; Bhoraskar, S.V.

    2002-01-01

    Full text: An intense source of oxygen finds important applications in many areas of science, technology and industry. It has been successfully used for surface activation and cleaning in the electronic, chemical and automotive industries. Atomic oxygen and interaction with materials have also a significant importance in space science and technology. This paper describes the detailed studies related to the surface modification and processing of different materials, which include metals and polymers by atomic oxygen produced in microwave assisted electron cyclotron resonance plasma. The energy distribution of ions was measured as a function of plasma parameters and density measurements were supplemented by catalytic probe using nickel and oxidation of silver surface

  12. Detection of atomic oxygen in flames by absorption spectroscopy

    International Nuclear Information System (INIS)

    Cheskis, S.; Kovalenko, S.A.

    1994-01-01

    The absolute concentration of atomic oxygen in an atmospheric pressure hydrogen/air flame has been measured using Intracavity Laser Spectroscopy (ICLS) based on a dye laser pumped by an argon-ion laser. Absorptions at the highly forbidden transitions at 630.030 nm and 636.380 nm were observed at an equivalent optical length of up to 10 km. The relatively low intensity of the dye laser avoids photochemical interferences that are inherent to some other methods for detecting atomic oxygen. The detection sensitivity is about 6x10 14 atom/cm 3 and can be improved with better flame and laser stabilization. (orig.)

  13. Free radicals, oxygen and radiosensitizing drugs: a very brief introduction

    International Nuclear Information System (INIS)

    Willson, R.

    1981-01-01

    A review is presented of the historical aspects of the search for radiation sensitizing drugs. Metronidazole, Flagyl and misonidazole are undergoing clincial trials as the result of basic free radical and cellular research. Studies at the molecular, biochemical and cellular levels are described. From the information obtained it now appears that several processes may be involved in sensitization: interference with charge recombination due to a sensitizer having a high electron affinity; an increase in the yield of oxidizing hydroxyl radicals by electron sequestration; interference with radical combination reactions due to a sensitizer having a high one electron oxidation potential; oxidation or organic radicals so fixing them; formation of products which are toxic; and changes in the biochemistry of the cell. 106 references, 4 figures

  14. CRC handbook of methods for oxygen radical research

    National Research Council Canada - National Science Library

    Greenwald, Robert A

    1985-01-01

    .... This volume is divided into five sections. Section I deals with preparative methodology for isolation and purification of the components of the oxy radical experimental systems used most frequently, including all the three forms of SOD...

  15. Resonances in Electron Impact on Atomic Oxygen

    International Nuclear Information System (INIS)

    Yang, Wang; Ya-Jun, Zhou; Li-Guang, Jiao; Ratnavelu, Kuru

    2008-01-01

    The momentum-space coupled-channels-optical (CCO) method is used to study the resonances in electron-oxygen collision in the energy region of 9–12eV. Present results have shown agreement with the available experimental and theoretical results, and new positions of resonances are found by the comparison of total cross sections. (fundamental areas of phenomenology (including applications))

  16. Exploring the dynamics of hydrogen atom release from the radical-radical reaction of O(3P) with C3H5

    International Nuclear Information System (INIS)

    Joo, Sun-Kyu; Kwon, Lee-Kyoung; Lee, Hohjai; Choi, Jong-Ho

    2004-01-01

    The gas-phase radical-radical reaction dynamics of O( 3 P)+C 3 H 5 →H( 2 S)+C 3 H 4 O was studied at an average collision energy of 6.4 kcal/mol in a crossed beam configuration. The ground-state atomic oxygen [O( 3 P)] and allyl radicals (C 3 H 5 ) were generated by the photolysis of NO 2 and the supersonic flash pyrolysis of allyl iodide, respectively. Nascent hydrogen atom products were probed by the vacuum-ultraviolet-laser induced fluorescence spectroscopy in the Lyman-α region centered at 121.6 nm. With the aid of the CBS-QB3 level of ab initio theory, it has been found that the barrierless addition of O( 3 P) to C 3 H 5 forms the energy-rich addition complexes on the lowest doublet potential energy surface, which are predicted to undergo a subsequent direct decomposition step leading to the reaction products H+C 3 H 4 O. The major counterpart C 3 H 4 O of the probed hydrogen atom is calculated to be acrolein after taking into account the factors of barrier height, reaction enthalpy, and the number of intermediates involved along the reaction pathway. The nascent H-atom Doppler profile analysis shows that the average center-of-mass translational energy of the H+C 3 H 4 O products and the fraction of the total available energy released as the translational energy were determined to be 3.83 kcal/mol and 0.054, respectively. On the basis of comparison with statistical calculations, the reaction proceeds through the formation of short-lived addition complexes rather than statistical, long-lived intermediates, and the polyatomic acrolein product is significantly internally excited at the moment of the decomposition

  17. Exploring the dynamics of hydrogen atom release from the radical-radical reaction of O(3P) with C3H5

    Science.gov (United States)

    Joo, Sun-Kyu; Kwon, Lee-Kyoung; Lee, Hohjai; Choi, Jong-Ho

    2004-05-01

    The gas-phase radical-radical reaction dynamics of O(3P)+C3H5→H(2S)+C3H4O was studied at an average collision energy of 6.4 kcal/mol in a crossed beam configuration. The ground-state atomic oxygen [O(3P)] and allyl radicals (C3H5) were generated by the photolysis of NO2 and the supersonic flash pyrolysis of allyl iodide, respectively. Nascent hydrogen atom products were probed by the vacuum-ultraviolet-laser induced fluorescence spectroscopy in the Lyman-α region centered at 121.6 nm. With the aid of the CBS-QB3 level of ab initio theory, it has been found that the barrierless addition of O(3P) to C3H5 forms the energy-rich addition complexes on the lowest doublet potential energy surface, which are predicted to undergo a subsequent direct decomposition step leading to the reaction products H+C3H4O. The major counterpart C3H4O of the probed hydrogen atom is calculated to be acrolein after taking into account the factors of barrier height, reaction enthalpy, and the number of intermediates involved along the reaction pathway. The nascent H-atom Doppler profile analysis shows that the average center-of-mass translational energy of the H+C3H4O products and the fraction of the total available energy released as the translational energy were determined to be 3.83 kcal/mol and 0.054, respectively. On the basis of comparison with statistical calculations, the reaction proceeds through the formation of short-lived addition complexes rather than statistical, long-lived intermediates, and the polyatomic acrolein product is significantly internally excited at the moment of the decomposition.

  18. Production of pulsed atomic oxygen beams via laser vaporization methods

    International Nuclear Information System (INIS)

    Brinza, D.E.; Coulter, D.R.; Liang, R.H.; Gupta, A.

    1987-01-01

    Energetic pulsed atomic oxygen beams were generated by laser-driven evaporation of cryogenically frozen ozone/oxygen films and thin films of indium-tin oxide (ITO). Mass and energy characterization of beams from the ozone/oxygen films were carried out by mass spectrometry. The peak flux, found to occur at 10 eV, is estimated from this data to be 3 x 10(20) m(-2) s(-1). Analysis of the time-of-flight data indicates a number of processes contribute to the formation of the atomic oxygen beam. The absence of metastable states such as the 2p(3) 3s(1) (5S) level of atomic oxygen blown off from ITO films is supported by the failure to observe emission at 777.3 nm from the 2p(3) 3p(1) (5P/sub J/) levels. Reactive scattering experiments with polymer film targets for atomic oxygen bombardment are planned using a universal crossed molecular beam apparatus

  19. Atom transfer radical polymerization of n-butyl acrylate catalyzed by atom transfer radical polymerization of n-butyl acrylate catalyzed by

    NARCIS (Netherlands)

    Zhang, H.; Linde, van der R.

    2002-01-01

    The homogeneous atom transfer radical polymerization (ATRP) of n-butyl acrylate with CuBr/N-(n-hexyl)-2-pyridylmethanimine as a catalyst and ethyl 2-bromoisobutyrate as an initiator was investigated. The kinetic plots of ln([M]0/[M]) versus the reaction time for the ATRP systems in different

  20. Excimer laser corneal surgery and free oxygen radicals.

    Science.gov (United States)

    Bilgihan, K; Bilgihan, A; Akata, F; Hasanreisoğlu, B; Türközkan, N

    1996-01-01

    Corneal photoablation with 193 nm argon fluoride excimer laser is a new technique for the treatment of refractive errors and for removing corneal opacities and irregularities. Ultraviolet radiation and thermal injury induce free radical formation in the tissues. The aim of this study was to confirm the production of free radicals by excimer laser photoablation in rabbits. The thermal changes of the posterior corneal surface were recorded during excimer laser photoablation. The lipid peroxide (LPO) levels and superoxide dismutase (SOD) activities of aqueous humour were measured after excimer laser keratectomy. The aqueous LPO levels were not changed after excimer laser ablation, but both the thermal increase in the cornea during the photoablation and the decreased aqueous SOD activities suggest that free radicals are formed in the cornea during excimer laser keratectomy, and that they may be responsible for some of the complications of excimer laser corneal surgery.

  1. Involvement of active oxygen in lipid peroxide radical reaction of epidermal homogenate following ultraviolet light exposure

    International Nuclear Information System (INIS)

    Nishi, J.; Ogura, R.; Sugiyama, M.; Hidaka, T.; Kohno, M.

    1991-01-01

    To elucidate the radical mechanism of lipid peroxidation induced by ultraviolet light (UV) irradiation, an electron spin resonance (ESR) study was made on epidermal homogenate prepared from albino rat skin. The exposure of the homogenate to UV light resulted in an increase in lipid peroxide content, which was proportional to the time of UV exposure. Using ESR spin trapping (dimethyl-1-pyrroline-N-oxide, DMPO), the DMPO spin adduct spectrum of lipid radicals (L.) was measured following UV exposure (DMPO-L.:aN = 15.5 G, aH = 22.7 G), as was the spectrum of DMPO-hydroxyl radical (DMPO-OH, aN = aH = 15.5 G). In the presence of superoxide dismutase, the DMPO spin adduct spectrum of lipid radicals was found to be reduced remarkably. Therefore, it was shown that the generation of the lipid radicals partially involves superoxide anion radicals, in addition to hydroxyl radicals. In the ESR free-radical experiment, an ESR signal appeared at g = 2.0064 when the ESR tube filled with homogenate was exposed to UV light at -150 degrees C. The temperature-dependent change in the ESR free radical signal of homogenate exposed to UV light was observed at temperatures varying from -150 degrees C to room temperature. By using degassed samples, it was confirmed that oxygen is involved in the formation of the lipid peroxide radicals (LOO.) from the lipid radicals (L.)

  2. Energetic Metastable Oxygen and Nitrogen Atoms in the Terrestrial Atmosphere

    Science.gov (United States)

    Kharchenko, Vasili; Dalgarno, A.

    2005-01-01

    This report summarizes our research performed under NASA Grant NAG5-11857. The three-year grant have been supported by the Geospace Sciences SR&T program. We have investigated the energetic metastable oxygen and nitrogen atoms in the terrestrial stratosphere, mesosphere and thermosphere. Hot atoms in the atmosphere are produced by solar radiation, the solar wind and various ionic reactions. Nascent hot atoms arise in ground and excited electronic states, and their translational energies are larger by two - three orders of magnitude than the thermal energies of the ambient gas. The relaxation kinetics of hot atoms determines the rate of atmospheric heating, the intensities of aeronomic reactions, and the rate of atom escape from the planet. Modeling of the non-Maxwellian energy distributions of metastable oxygen and nitrogen atoms have been focused on the determination of their impact on the energetics and chemistry of the terrestrial atmosphere between 25 and 250 km . At this altitudes, we have calculated the energy distribution functions of metastable O and N atoms and computed non-equilibrium rates of important aeronomic reactions, such as destruction of the water molecules by O(1D) atoms and production of highly excited nitric oxide molecules. In the upper atmosphere, the metastable O(lD) and N(2D) play important role in formation of the upward atomic fluxes. We have computed the upward fluxes of the metastable and ground state oxygen atoms in the upper atmosphere above 250 km. The accurate distributions of the metastable atoms have been evaluated for the day and night-time conditions.

  3. Effects of oxygen radical scavengers on the inactivation of SS phi X174 DNA by the semi-quinone free radical of the antitumor agent etoposide

    NARCIS (Netherlands)

    van Maanen, M.J.; Mans, D.R.A.; Lafleur, M.V.M.; Van Schaik, M A; de Vries, J; Vermeulen, N P; Retèl, J.; Lankelma, J

    1990-01-01

    We have studied the effects of oxygen radical scavengers on the inactivation of ss phi X174 DNA by the semi-quinone free radical of the antitumor agent etoposide (VP 16-213), which was generated from the ortho-quinone of etoposide at pH greater than or equal to 7.4. A semi-quinone free radical of

  4. Radical Chemistry and Charge Manipulation with an Atomic Force Microscope

    Science.gov (United States)

    Gross, Leo

    The fuctionalization of tips by atomic manipulation dramatically increased the resolution of atomic force microscopy (AFM). The combination of high-resolution AFM with atomic manipulation now offers the unprecedented possibility to custom-design individual molecules by making and breaking bonds with the tip of the microscope and directly characterizing the products on the atomic scale. We recently applied this technique to generate and study reaction intermediates and to investigate chemical reactions trigged by atomic manipulation. We formed diradicals by dissociating halogen atoms and then reversibly triggered ring-opening and -closing reactions via atomic manipulation, allowing us to switch and control the molecule's reactivity, magnetic and optical properties. Additional information about charge states and charge distributions can be obtained by Kelvin probe force spectroscopy. On multilayer insulating films we investigated single-electron attachment, detachment and transfer between individual molecules. EU ERC AMSEL (682144), EU project PAMS (610446).

  5. Reaction kinetics of hydrogen atom abstraction from isopentanol by the H atom and HO2˙ radical.

    Science.gov (United States)

    Parab, Prajakta Rajaram; Heufer, K Alexander; Fernandes, Ravi Xavier

    2018-04-25

    Isopentanol is a potential next-generation biofuel for future applications to Homogeneous Charge Compression Ignition (HCCI) engine concepts. To provide insights into the combustion behavior of isopentanol, especially to its auto-ignition behavior which is linked both to efficiency and pollutant formation in real combustion systems, detailed quantum chemical studies for crucial reactions are desired. H-Abstraction reaction rates from fuel molecules are key initiation steps for chain branching required for auto-ignition. In this study, rate constants are determined for the hydrogen atom abstraction reactions from isopentanol by the H atom and HO2˙ radical by implementing the CBS-QB3 composite method. For the treatment of the internal rotors, a Pitzer-Gwinn-like approximation is applied. On comparing the computed reaction energies, the highest exothermicity (ΔE = -46 kJ mol-1) is depicted for Hα abstraction by the H atom whereas the lowest endothermicity (ΔE = 29 kJ mol-1) is shown for the abstraction of Hα by the HO2˙ radical. The formation of hydrogen bonding is found to affect the kinetics of the H atom abstraction reactions by the HO2˙ radical. Further above 750 K, the calculated high pressure limit rate constants indicate that the total contribution from delta carbon sites (Cδ) is predominant for hydrogen atom abstraction by the H atom and HO2˙ radical.

  6. Single Photon Double Ionization of Atomic Oxygen

    Science.gov (United States)

    Wickramarathna, Madhushani; Gorczyca, Thomas; Ballance, Connor; Stolte, Wayne

    2017-04-01

    Single photon double ionization cross sections are calculated using an R-matrix with pseudostates (RMPS) method which was recently applied by Gorczyca et al. for the double photoionization of helium. With the convergence of these theoretical calculations for the simple case of helium, we extend this methodology to consider the more complex case of oxygen double photoionization. We compare our calculated results with recent measurements at the Advanced Light Source, as well as earlier experimental measurements. Our RMPS results agree well, qualitatively, with the experimental measurements, but there exist outstanding discrepancies to be addressed. This project is supported by NASA APRA award NNX17AD41G.

  7. Proceedings of the NASA workshop on atomic oxygen effects

    International Nuclear Information System (INIS)

    Brinza, D.E.

    1987-06-01

    A workshop was held to address the scientific issues concerning the effects of atomic oxygen on materials in the low Earth orbital (LEO) environment. The program included 18 invited speakers plus contributed posters covering topics such as LEO spaceflight experiments, interaction mechanisms, and atomic oxygen source development. Discussion sessions were also held to organize a test program to evaluate atomic oxygen exposure facilities. The key issues raised in the workshop were: (1) the need to develop a reliable predictive model of the effects of long-term exposure of materials to the LEO environment; (2) the ability of ground-based exposure facilities to provide useful data for development of durable materials; and (3) accurate determination of the composition of the LEO environment. These proceedings include the invited papers, the abstracts for the contributed posters, and an account of the test program discussion sessions

  8. Cleaning of Fire Damaged Watercolor and Textiles Using Atomic Oxygen

    Science.gov (United States)

    Rutledge, Sharon K.; Banks, Bruce A.; Chichernea, Virgil A.; Haytas, Christy A.

    2000-01-01

    A noncontact technique is described that uses atomic oxygen generated under low pressure in the presence of nitrogen to remove soot from the surface of a test watercolor panel and strips of cotton, wool and silk. The process, which involves surface oxidation, permits control of the amount of surface material removed. The effectiveness of soot removal from test panels of six basic watercolors (alizarin crimson, burnt sienna, lemon yellow, yellow ochre, cerulean blue and ultramarine blue) and strips of colored cotton, wool and silk was measured using reflectance spectroscopy. The atomic oxygen removed soot effectively from the treated areas and enabled partial recovery of charred watercolors. However, overexposure can result in removal of sizing, bleaching, and weakening of the structure. With the proper precautions, atomic oxygen treatment appears to have great potential to salvage heavily smoke damaged artworks which were previously considered unrestorable.

  9. Multi-functional magnesium alloys containing interstitial oxygen atoms.

    Science.gov (United States)

    Kang, H; Choi, H J; Kang, S W; Shin, S E; Choi, G S; Bae, D H

    2016-03-15

    A new class of magnesium alloys has been developed by dissolving large amounts of oxygen atoms into a magnesium lattice (Mg-O alloys). The oxygen atoms are supplied by decomposing titanium dioxide nanoparticles in a magnesium melt at 720 °C; the titanium is then completely separated out from the magnesium melt after solidification. The dissolved oxygen atoms are located at the octahedral sites of magnesium, which expand the magnesium lattice. These alloys possess ionic and metallic bonding characteristics, providing outstanding mechanical and functional properties. A Mg-O-Al casting alloy made in this fashion shows superior mechanical performance, chemical resistance to corrosion, and thermal conductivity. Furthermore, a similar Mg-O-Zn wrought alloy shows high elongation to failure (>50%) at room temperature, because the alloy plastically deforms with only multiple slips in the sub-micrometer grains (alloys are expected to open a new paradigm in commercial alloy design.

  10. Structure and Reactivity of the Glutathione Radical Cation: Radical Rearrangement from the Cysteine Sulfur to the Glutamic Acid alpha-Carbon Atom

    NARCIS (Netherlands)

    Osburn, S.; Berden, G.; Oomens, J.; Gulyuz, K.; Polfer, N.C.; O'Hair, R.A.J.; Ryzhov, V.

    2013-01-01

    A gas-phase radical rearrangement through intramolecular hydrogen-atom transfer (HAT) was studied in the glutathione radical cation, [-ECG](+.), which was generated by a homolytic cleavage of the protonated S-nitrosoglutathione. Ion-molecule reactions suggested that the radical migrates from the

  11. Atomic Oxygen Erosion Yield Dependence Upon Texture Development in Polymers

    Science.gov (United States)

    Banks, Bruce A.; Loftus, Ryan J.; Miller, Sharon K.

    2016-01-01

    The atomic oxygen erosion yield (volume of a polymer that is lost due to oxidation per incident atom) of polymers is typically assumed to be reasonably constant with increasing fluence. However polymers containing ash or inorganic pigments, tend to have erosion yields that decrease with fluence due to an increasing presence of protective particles on the polymer surface. This paper investigates two additional possible causes for erosion yields of polymers that are dependent upon atomic oxygen. These are the development of surface texture which can cause the erosion yield to change with fluence due to changes in the aspect ratio of the surface texture that develops and polymer specific atomic oxygen interaction parameters. The surface texture development under directed hyperthermal attack produces higher aspect ratio surface texture than isotropic thermal energy atomic oxygen attack. The fluence dependence of erosion yields is documented for low Kapton H (DuPont, Wilmington, DE) effective fluences for a variety of polymers under directed hyperthermal and isotropic thermal energy attack.

  12. Atomic oxygen-MoS sub 2 chemical interactions

    Energy Technology Data Exchange (ETDEWEB)

    Cross, J.B.; Martin, J.A. (Los Alamos National Lab., NM (USA)); Pope, L.E. (Sandia National Labs., Albuquerque, NM (USA)); Koontz, S.L. (National Aeronautics and Space Administration, Johnson Space Center, Houston, TX (USA))

    1990-10-01

    The present study shows that an O-atom translation energy of 1.5 eV, SO{sub 2} is generated and outgases from an anhydrous MoS{sub 2} surface with an initial reactivity nearly 50% that of kapton. The reaction of atomic oxygen with MoS{sub 2} has little or no translational energy barrier, i.e. thermally generated atomic oxygen reacts as readily as that having 1.5 eV of translational energy. For MoS{sub 2} films sputter-deposited at 50-70deg C, friction measurements showed a high initial friction coefficient (up to 0.25) for MoS{sub 2} surfaces exposed to atomic oxygen, which dropped to the normal low values after several cycles of operation in air and ultrahigh vacuum. For MoS{sub 2} films deposited at 200deg C, the friction coefficient was not affected by the O-atom exposure. (orig.).

  13. Role of oxygen free radicals in the induction of sister chromatid exchanges by cigarette smoke

    International Nuclear Information System (INIS)

    Lee, C.K.; Brown, B.G.; Rice, W.Y. Jr.; Doolittle, D.J.

    1989-01-01

    Cigarette smoke has been reported to contain free radicals and free radical generators in both the gas and particulate phases. Studies in our laboratory have shown that both cigarette smoke condensate (CSC) and smoke bubbled through phosphate buffered saline solution (smoke-PBS) increased sister chromatid exchanges (SCE) in Chinese hamster ovary cells in a dose-dependent manner. Since oxygen free radicals have been shown to cause SCEs and other chromosomal damage, we investigated the role of these radicals in the induction of SCEs by CSC and smoke-PBS. Addition of the antioxidant enzymes catalase and superoxide dismutase or the oxygen-radical scavenger ascorbic acid failed to reduce the SCE frequency in the presence of either CSC or smoke-PBS. Additional studies indicated that the quantity of hydrogen peroxide produced in CSC or smoke-PBS is too small to account for the observed SCE induction. It appears, therefore, that SCE induction by CSC or smoke-PBS does not involve the participation of oxygen free radicals

  14. The scavenger activities of tea polyphenol and quercetin against oxygen radicals

    International Nuclear Information System (INIS)

    Fang Ruoying; Cheng Jiwu; Hu Tianxi; Tu Tiecheng; Dong Jirong; Wang Wenfeng; Lin nianyun

    1992-01-01

    Studies of free radical biology and medicine have shown that carcinogenesis, vascular diseases of heart and brain, radiation injuries, ageing etc are strictly correlated with free radical injury of tissues. Thus, pharmacologists and biologists are focusing attention on searching for scavengers, especially naturally occurring antioxidant of oxidizing free radicals. Previous studies have indicated that phenolic antioxidants have efficient scavenger activities. Utilizing following methods including chemical luminescence, ESR spectroscopy and pulse radiolysis techniques the scavenger activities of tea polyphenols and quercetin against active species of oxygen have been studied

  15. Photoionization cross section of atomic and molecular oxygen

    International Nuclear Information System (INIS)

    Pareek, P.N.

    1983-01-01

    Photoionization cross sections of atomic oxygen and dissociative photoionization cross sections of molecular oxygen were measured from their respective thresholds to 120 angstrom by use of a photoionization mass spectrometer in conjunction with a spark light source. The photoionization cross sections O 2 + parent ion and O + fragment ion from neutral O 2 were obtained by a technique that eliminated the serious problem of identifying the true abundances of O + ions. These ions are generally formed with considerable kinetic energy and, because most mass spectrometers discriminate against energetic ions, true O + abundances are difficult to obtain. In the present work the relative cross sections for producing O + ions are obtained and normalized against the total cross sections in a spectral region where dissociative ionization is not possible. The fragmentation cross sections for O + were then obtained by subtraction of O 2 + cross sections from the known total photoionization cross sections. The results are compared with the previously published measurements. The absolute photoionization cross section of atomic oxygen sigma 8 /sub +/ was measured at 304 A. The actual number density of oxygen atoms within the ionization region was obtained by measuring the fraction of 0 2 molecules dissociated. This sigma/sub +/ at 304 angstrom was used to convert the relative photoinization cross sections, measured as a function of wavelength using a calibrated photodiode, to absolute cross sections. The results are compared with previous measurements and calculated cross sections. angstrom Rydberg series converging to the OII 4 P state was observed

  16. High performance platinum single atom electrocatalyst for oxygen reduction reaction

    Science.gov (United States)

    Liu, Jing; Jiao, Menggai; Lu, Lanlu; Barkholtz, Heather M.; Li, Yuping; Wang, Ying; Jiang, Luhua; Wu, Zhijian; Liu, Di-Jia; Zhuang, Lin; Ma, Chao; Zeng, Jie; Zhang, Bingsen; Su, Dangsheng; Song, Ping; Xing, Wei; Xu, Weilin; Wang, Ying; Jiang, Zheng; Sun, Gongquan

    2017-07-01

    For the large-scale sustainable implementation of polymer electrolyte membrane fuel cells in vehicles, high-performance electrocatalysts with low platinum consumption are desirable for use as cathode material during the oxygen reduction reaction in fuel cells. Here we report a carbon black-supported cost-effective, efficient and durable platinum single-atom electrocatalyst with carbon monoxide/methanol tolerance for the cathodic oxygen reduction reaction. The acidic single-cell with such a catalyst as cathode delivers high performance, with power density up to 680 mW cm-2 at 80 °C with a low platinum loading of 0.09 mgPt cm-2, corresponding to a platinum utilization of 0.13 gPt kW-1 in the fuel cell. Good fuel cell durability is also observed. Theoretical calculations reveal that the main effective sites on such platinum single-atom electrocatalysts are single-pyridinic-nitrogen-atom-anchored single-platinum-atom centres, which are tolerant to carbon monoxide/methanol, but highly active for the oxygen reduction reaction.

  17. Gastric injury induced by hemorrhage, local ischemia, and oxygen radical generation

    International Nuclear Information System (INIS)

    Wadhwa, S.S.; Perry, M.A.

    1987-01-01

    Gastric mucosal injury caused by local intra-arterial generation of oxygen-derived free radicals was compared with gastric injury caused by 30 min of hemorrhage-induced ischemia or local ischemia. The index of injury was the loss of 51 Cr-labeled red cells across the gastric mucosa. Generation of oxygen radicals in the celiac artery caused a rapid increase in mucosal blood loss during the period of radical generation, and this loss was maintained after radical production ceased. Local ischemia produced similar mucosal injury; however, this occurred after reperfusion of the stomach and not during the ischemic episode. Hemorrhage-induced ischemia produced a threefold greater mucosal blood loss than local ischemia. The results of this study indicate that (1) oxygen radicals generated enzymatically in the blood supply to the stomach cause mucosal bleeding of similar magnitude to that observed after local ischemia and (2) that gastric ischemia induced by systemic hypotension produces more severe gastric injury than the same level of local hypotension

  18. Development of sensors for monitoring oxygen and free radicals in plant physiology

    Science.gov (United States)

    Chaturvedi, Prachee

    Oxygen plays a critical role in the physiology of photosynthetic organisms, including bioenergetics, metabolism, development, and stress response. Oxygen levels affect photosynthesis, respiration, and alternative oxidase pathways. Likewise, the metabolic rate of spatially distinct plant cells (and therefore oxygen flux) is known to be affected by biotic stress (e.g., herbivory) and environmental stress (e.g., salt/nutrient stress). During aerobic metabolism, cells produce reactive oxygen species (ROS) as a by product. Plants also produce ROS during adaptation to stress (e.g., abscisic acid (ABA) mediated stress responses). If stress conditions are prolonged, ROS levels surpass the capacity of detoxifying mechanisms within the cell, resulting in oxidative damage. While stress response pathways such as ABA-mediated mechanisms have been well characterized (e.g., water stress, inhibited shoot growth, synthesis of storage proteins in seeds), the connection between ROS production, oxygen metabolism and stress response remains unknown. In part, this is because details of oxygen transport at the interface of cell(s) and the surrounding microenvironment remains nebulous. The overall goal of this research was to develop oxygen and Free radical sensors for studying stress signaling in plants. Recent developments in nanomaterials and data acquisition systems were integrated to develop real-time, non-invasive oxygen and Free radical sensors. The availability of these sensors for plant physiologists is an exciting opportunity to probe the functional realm of cells and tissues in ways that were not previously possible.

  19. Effects of Actinobacillus pleuropneumoniae cytotoxins on generation of oxygen radicals by porcine neutrophils

    Directory of Open Access Journals (Sweden)

    Simson Tarigan

    1999-03-01

    Full Text Available Cytotoxins produced by Actinobacillus pleuropneumoniae (App suggested to be the most important pathogenic and virulent factors for this organism. However, the mechanisms on how the cytotoxins contribute to the disease process remain unclear. The purpose of this study is to investigate the effect of the cytotoxins on the oxidative-burst metabolism of porcine neutrophils. In this study, neutrophils were firstly loaded with an oxidative probe dichlorofluorescin diacetate (DCFHDA then expose to cytotoxins. Cells producing oxygen radicals emitted fluorescence and its intensity was measured with a FACScan flow cytometer. All cytotoxins derived from either App serotypes producing ApxI and ApxII, App serotypes producing ApxII only, or App serotypes producing ApxII and ApxIII were capable of stimulating neutrophils for oxygen-radical generation. However, compared with phorbol myristate acetate (PMA, App cytotoxins were much weaker as stimulants for oxygen radicals. In addition, Apx preparation stimulated an oxidative-burst metabolism of neutrophils at a low, narrow range of Apx doses. At higher doses, the toxins inhibit the oxidative burst metabolism. The effects of cytotoxins produced by App during infection on recruited neutrophils into the lungs are assumed to be comparable to those observed in this in vitro study. Neutrophils, and other host cells, adjacent to the bacteria become lysis due to high toxin concentration, whereas those at some distance to the bacteria produce oxygen radicals which in turn cause tissue damage or necrosis.

  20. Induction of oxygen free radical generation in human monocytes by lipoprotein(a)

    DEFF Research Database (Denmark)

    Riis Hansen, P; Kharazmi, A; Jauhiainen, M

    1994-01-01

    The mechanism behind the association of elevated plasma lipoprotein(a) [Lp(a)] levels with atherosclerotic disease is unknown. In the present study, Lp(a) induced generation of oxygen free radicals by monocytes from selected healthy individuals in vitro. This observation may provide a link between...

  1. PREFACE: Light element atom, molecule and radical behaviour in the divertor and edge plasma regions

    Science.gov (United States)

    Braams, Bastiaan J.; Chung, Hyun-Kung

    2015-01-01

    This volume of Journal of Physics: Conference Series contains contributions by participants in an International Atomic Energy Agency (IAEA) Coordinated Research Project (CRP) on "Light element atom, molecule and radical behaviour in the divertor and edge plasma regions" (in magnetic fusion devices). Light elements are the dominant impurity species in fusion experiments and in the near-wall plasma they occur as atoms or ions and also as hydrides and other molecules and molecular ions. Hydrogen (H or D, and T in a reactor) is the dominant species in fusion experiments, but all light elements He - O and Ne are of interest for various reasons. Helium is a product of the D+T fusion reaction and is introduced in experiments for transport studies. Lithium is used for wall coating and also as a beam diagnostic material. Beryllium is foreseen as a wall material for the ITER experiment and is used on the Joint European Torus (JET) experiment. Boron may be used as a coating material for the vessel walls. Carbon (graphite or carbon-fiber composite) is often used as the target material for wall regions subject to high heat load. Nitrogen may be used as a buffer gas for edge plasma cooling. Oxygen is a common impurity in experiments due to residual water vapor. Finally, neon is another choice as a buffer gas. Data for collisional and radiative processes involving these species are important for plasma modelling and for diagnostics. The participants in the CRP met 3 times over the years 2009-2013 for a research coordination meeting. Reports and presentation materials for these meetings are available through the web page on coordinated research projects of the (IAEA) Atomic and Molecular Data Unit [1]. Some of the numerical data generated in the course of the CRP is available through the ALADDIN database [2]. The IAEA takes the opportunity to thank the participants in the CRP for their dedicated efforts in the course of the CRP and for their contributions to this volume. The IAEA

  2. A Comprehensive X-Ray Absorption Model for Atomic Oxygen

    Science.gov (United States)

    Gorczyca, T. W.; Bautista, M. A.; Hasoglu, M. F.; Garcia, J.; Gatuzz, E.; Kaastra, J. S.; Kallman, T. R.; Manson, S. T.; Mendoza, C.; Raassen, A. J. J.; hide

    2013-01-01

    An analytical formula is developed to accurately represent the photoabsorption cross section of atomic Oxygen for all energies of interest in X-ray spectral modeling. In the vicinity of the K edge, a Rydberg series expression is used to fit R-matrix results, including important orbital relaxation effects, that accurately predict the absorption oscillator strengths below threshold and merge consistently and continuously to the above-threshold cross section. Further, minor adjustments are made to the threshold energies in order to reliably align the atomic Rydberg resonances after consideration of both experimental and observed line positions. At energies far below or above the K-edge region, the formulation is based on both outer- and inner-shell direct photoionization, including significant shake-up and shake-off processes that result in photoionization-excitation and double-photoionization contributions to the total cross section. The ultimate purpose for developing a definitive model for oxygen absorption is to resolve standing discrepancies between the astronomically observed and laboratory-measured line positions, and between the inferred atomic and molecular oxygen abundances in the interstellar medium from XSTAR and SPEX spectral models.

  3. Novel fluorinated block copolymer architectures fuelled by atom transfer radical polymerization

    DEFF Research Database (Denmark)

    Jankova, Katja; Hvilsted, Søren

    2005-01-01

    Block copolymers based on poly(pentafluorostyrene), PFS, in various numbers and of different lengths, and polystyrene are prepared by atom transfer radical polymerization (ATRP). Di- and triblock copolymers with varying amounts of PFS were synthesized employing either I phenylethylbromide or 1,4-...

  4. Atom-transfer radical polymerization of methyl methacrylate (MMA) using CuSCN as the catalyst

    NARCIS (Netherlands)

    Singha, N.K.; Klumperman, B.

    2000-01-01

    The effect of CuSCN as a catalyst in atom-transfer radical polymerization (ATRP) was investigated. CuSCN can successfully be used for the ATRP of MMA. Substituted bipyridines as well as imines can be used to stabilize the copper complex in solution. CuSCN induces faster polymerization compared to

  5. On Surface-Initiated Atom Transfer Radical Polymerization Using Diazonium Chemistry To Introduce the Initiator Layer

    DEFF Research Database (Denmark)

    Iruthayaraj, Joseph; Chernyy, Sergey; Lillethorup, Mie

    2011-01-01

    This work features the controllability of surface-initiated atom transfer radical polymerization (SI-ATRP) of methyl methacrylate, initiated by a multilayered 2-bromoisobutyryl moiety formed via diazonium chemistry. The thickness as a function of polymerization time has been studied by varying di...

  6. The effect of reducing monosaccharides on the atom transfer radical polymerization of butyl methacrylate

    NARCIS (Netherlands)

    Vries, de Andrew; Klumperman, B.; Wet-Roos, de D.; Sanderson, R.D.

    2001-01-01

    The effect of various reducing monosaccharides on the rate of atom transfer radical polymerization (ATRP) of butyl methacrylate is reported in this study. The addition of reducing sugars affects the rate of ATRP positively with a 100% increase in the rate of polymerization in some cases. In

  7. Polymer coating comprising 2-methoxyethyl acrylate units synthesized by surface-initiated atom transfer radical polymerization

    DEFF Research Database (Denmark)

    2011-01-01

    Source: US2012184029A The present invention relates to preparation of a polymer coating comprising or consisting of polymer chains comprising or consisting of units of 2-methoxyethyl acrylate synthesized by Surface-Initiated Atom Transfer Radical Polymerization (SI ATRP) such as ARGET SI ATRP...

  8. Hydrolysis of 4-Acetoxystyrene Polymers Prepared by Atom Transfer Radical Polymerization

    DEFF Research Database (Denmark)

    Chen, Xianyi; Jankova, Katja; Kops, Jørgen

    1999-01-01

    Hydrolysis of 4-acetoxystyrene polymers prepared by atom transfer radical polymerization was carried out under various reaction conditions. It was found that hydrazinolysis of 4-acetoxystyrene homopolymers, random and block copolymers with styrene in 1,4-dioxane, afforded the corresponding narrow...

  9. Surface-initiated Atom Transfer Radical Polymerization - a Technique to Develop Biofunctional Coatings

    DEFF Research Database (Denmark)

    Fristrup, Charlotte Juel; Jankova Atanasova, Katja; Hvilsted, Søren

    2009-01-01

    The initial formation of initiating sites for atom transfer radical polymerization (ATRP) on various polymer surfaces and numerous inorganic and metallic surfaces is elaborated. The subsequent ATRP grafting of a multitude of monomers from such surfaces to generate thin covalently linked polymer...

  10. Organic thin film transistors with polymer brush gate dielectrics synthesized by atom transfer radical polymerization

    DEFF Research Database (Denmark)

    Pinto, J.C.; Whiting, G.L.; Khodabakhsh, S.

    2008-01-01

    , synthesized by atom transfer radical polymerization (ATRP), were used to fabricate low voltage OFETs with both evaporated pentacene and solution deposited poly(3-hexylthiophene). The semiconductor-dielectric interfaces in these systems were studied with a variety of methods including scanning force microscopy...

  11. Free radicals, reactive oxygen species, oxidative stress and its classification.

    Science.gov (United States)

    Lushchak, Volodymyr I

    2014-12-05

    Reactive oxygen species (ROS) initially considered as only damaging agents in living organisms further were found to play positive roles also. This paper describes ROS homeostasis, principles of their investigation and technical approaches to investigate ROS-related processes. Especial attention is paid to complications related to experimental documentation of these processes, their diversity, spatiotemporal distribution, relationships with physiological state of the organisms. Imbalance between ROS generation and elimination in favor of the first with certain consequences for cell physiology has been called "oxidative stress". Although almost 30years passed since the first definition of oxidative stress was introduced by Helmut Sies, to date we have no accepted classification of oxidative stress. In order to fill up this gape here classification of oxidative stress based on its intensity is proposed. Due to that oxidative stress may be classified as basal oxidative stress (BOS), low intensity oxidative stress (LOS), intermediate intensity oxidative stress (IOS), and high intensity oxidative stress (HOS). Another classification of potential interest may differentiate three categories such as mild oxidative stress (MOS), temperate oxidative stress (TOS), and finally severe (strong) oxidative stress (SOS). Perspective directions of investigations in the field include development of sophisticated classification of oxidative stresses, accurate identification of cellular ROS targets and their arranged responses to ROS influence, real in situ functions and operation of so-called "antioxidants", intracellular spatiotemporal distribution and effects of ROS, deciphering of molecular mechanisms responsible for cellular response to ROS attacks, and ROS involvement in realization of normal cellular functions in cellular homeostasis. Copyright © 2014 Elsevier Ireland Ltd. All rights reserved.

  12. Synoviocytes, not chondrocytes, release free radicals after cycles of anoxia/re-oxygenation

    International Nuclear Information System (INIS)

    Schneider, Nicole; Mouithys-Mickalad, Ange L.; Lejeune, Jean-Philippe; Deby-Dupont, Ginette P.; Hoebeke, Maryse; Serteyn, Didier A.

    2005-01-01

    By oxymetry and electron paramagnetic resonance (EPR), we investigated the effects of repeated anoxia/re-oxygenation (A/R) periods on the respiration and production of free radicals by synoviocytes (rabbit HIG-82 cell line and primary equine synoviocytes) and equine articular chondrocytes. Three periods of 20 min anoxia followed by re-oxygenation were applied to 10 7 cells; O 2 consumption was measured before anoxia and after each re-oxygenation. After the last A/R, cellular free radical formation was investigated by EPR spectroscopy with spin trapping technique (n = 3 for each cell line). Both types of synoviocytes showed a high O 2 consumption, which was slowered after anoxia. By EPR with the spin trap POBN, we proved a free radical formation. Results were similar for equine and rabbit synoviocytes. For chondrocytes, we observed a low O 2 consumption, unchanged by anoxia, and no free radical production. These observations suggest an oxidant activity of synoviocytes, potentially important for the onset of osteoarthritis

  13. Functionalised Oximes: Emergent Precursors for Carbon-, Nitrogen- and Oxygen-Centred Radicals

    Directory of Open Access Journals (Sweden)

    John C. Walton

    2016-01-01

    Full Text Available Oxime derivatives are easily made, are non-hazardous and have long shelf lives. They contain weak N–O bonds that undergo homolytic scission, on appropriate thermal or photochemical stimulus, to initially release a pair of N- and O-centred radicals. This article reviews the use of these precursors for studying the structures, reactions and kinetics of the released radicals. Two classes have been exploited for radical generation; one comprises carbonyl oximes, principally oxime esters and amides, and the second comprises oxime ethers. Both classes release an iminyl radical together with an equal amount of a second oxygen-centred radical. The O-centred radicals derived from carbonyl oximes decarboxylate giving access to a variety of carbon-centred and nitrogen-centred species. Methods developed for homolytically dissociating the oxime derivatives include UV irradiation, conventional thermal and microwave heating. Photoredox catalytic methods succeed well with specially functionalised oximes and this aspect is also reviewed. Attention is also drawn to the key contributions made by EPR spectroscopy, aided by DFT computations, in elucidating the structures and dynamics of the transient intermediates.

  14. Optical emissions from oxygen atom reactions with adsorbates

    Science.gov (United States)

    Oakes, David B.; Fraser, Mark E.; Gauthier-Beals, Mitzi; Holtzclaw, Karl W.; Malonson, Mark; Gelb, Alan H.

    1992-12-01

    Although most optical materials are inert to the ambient low earth orbit environment, high velocity oxygen atoms will react with adsorbates to produce optical emissions from the ultraviolet into the infrared. The adsorbates arise from chemical releases or outgassing from the spacecraft itself. We have been investigating kinetic and spectral aspects of these phenomenon by direct observation of the 0.2 to 13 micrometers chemiluminescence from the interaction of a fast atomic oxygen beam with a continuously dosed surface. The dosing gases include fuels, combustion products and outgassed species such as unsymmetrical dimethylhydrazine (UDMH), NO, H2O and CO. The surface studied include gold and magnesium fluoride. In order to relate the results to actual spacecraft conditions these phenomena have been explored as a function of O atom velocity, dosant flux and substrate temperature. UDMH dosed surfaces exhibit spectra typical (wavelength and intensity) of carbonaceous surfaces. The primary emitters are CO, CO2, and OH. H2O dosed surfaces are dominated by OH and /or H2O emission while CO dosed surfaces are dominated by CO and CO2 emissions. The nitric oxide dosed surface produces a glow from 0.4 to 5.4 micrometers due to NO2* continuum emission. The emission was observed to increase by a factor of two upon cooling the surface from 20 degree(s)C to -35 degree(s)C.

  15. An atomic oxygen device based on PIG oxygen negative ion source

    International Nuclear Information System (INIS)

    Yu Jinxiang; Cai Minghui; Han Jianwei

    2008-01-01

    It is an important research subject for the spaceflight countries to conduct equivalent simulation of 5 eV atomic oxygen effects for the spaceflight material in low earth orbit. This paper introduces an apparatus used for producing atomic oxygen, which consists of a PIG ion source with permanent magnet, two electrodes extraction system, an electron deflector, an einzel lens, an ion decelerating electrode and a sample bracket. At present it has been used on the small debris accelerator in the Center for Space Science and Applied Research, Chinese Academy of Sciences, and the producing experiments of O - are carried out. 200-300μA of O - ions are extracted at the extraction voltage of 2-3 kV. The experiments for decelerating of O - ions and erosion of kapton foil are carried out also. Because of the target room used for both the atomic oxygen device and the small debris accelerator, the facility can be used for small debris impinging and atomic erosion for spaceflight materials simultaneously. (authors)

  16. Atomic oxygen ions as ionospheric biomarkers on exoplanets

    Science.gov (United States)

    Mendillo, Michael; Withers, Paul; Dalba, Paul A.

    2018-04-01

    The ionized form of atomic oxygen (O+) is the dominant ion species at the altitude of maximum electron density in only one of the many ionospheres in our Solar System — Earth's. This ionospheric composition would not be present if oxygenic photosynthesis was not an ongoing mechanism that continuously impacts the terrestrial atmosphere. We propose that dominance of ionospheric composition by O+ ions at the altitude of maximum electron density can be used to identify a planet in orbit around a solar-type star where global-scale biological activity is present. There is no absolute numerical value required for this suggestion of an atmospheric plasma biomarker — only the dominating presence of O+ ions at the altitude of peak electron density.

  17. K-shell auger decay of atomic oxygen

    Energy Technology Data Exchange (ETDEWEB)

    Stolte, W.C.; Lu, Y.; Samson, J.A.R. [Univ. of Nebraska, Lincoln, NE (United States)] [and others

    1997-04-01

    The aim of the present research is to understand the interaction between the ejected photoelectron and Auger electron produced by the Auger decay of a 1s hole in atomic oxygen, and to understand the influence this interaction has on the shape of the ionization cross sections. To accomplish this the authors have measured the relative ion yields (ion/photon) in the vicinity of the oxygen K-shell (525 - 533 eV) for O{sup +} and O{sup 2+}. The measurements were performed at the ALS on beamline, 6.3.2. The atomic oxygen was produced by passing molecular oxygen through a microwave-driven discharge. A Rydberg analysis of the two series leading to the [1s]2s{sup 2}2p{sup 4}({sup 4}P) and [1s]2s{sup 2}2p{sup 4}({sup 2}P) limits were obtained. This analysis shows some differences to the recently published results by Menzel et al. The energy position of the main 1s{sup 1}2s{sup 2}2p{sup 5}({sup 3}P) resonance differs by approximately 1 eV from the authors value, all members of the ({sup 2}P)np series differ by 0.3 eV, but the members of the ({sup 4}P)np series agree. The molecular resonance at 530.5 eV and those between 539 eV and 543 eV, measured with the microwave discharge off show identical results in both experiments.

  18. HFE gene variants and iron-induced oxygen radical generation in idiopathic pulmonary fibrosis.

    Science.gov (United States)

    Sangiuolo, Federica; Puxeddu, Ermanno; Pezzuto, Gabriella; Cavalli, Francesco; Longo, Giuliana; Comandini, Alessia; Di Pierro, Donato; Pallante, Marco; Sergiacomi, Gianluigi; Simonetti, Giovanni; Zompatori, Maurizio; Orlandi, Augusto; Magrini, Andrea; Amicosante, Massimo; Mariani, Francesca; Losi, Monica; Fraboni, Daniela; Bisetti, Alberto; Saltini, Cesare

    2015-02-01

    In idiopathic pulmonary fibrosis (IPF), lung accumulation of excessive extracellular iron and macrophage haemosiderin may suggest disordered iron homeostasis leading to recurring microscopic injury and fibrosing damage. The current study population comprised 89 consistent IPF patients and 107 controls. 54 patients and 11 controls underwent bronchoalveolar lavage (BAL). Haemosiderin was assessed by Perls' stain, BAL fluid malondialdehyde (MDA) by high-performance liquid chromatography, BAL cell iron-dependent oxygen radical generation by fluorimetry and the frequency of hereditary haemochromatosis HFE gene variants by reverse dot blot hybridisation. Macrophage haemosiderin, BAL fluid MDA and BAL cell unstimulated iron-dependent oxygen radical generation were all significantly increased above controls (pHFE allelic variants was markedly higher in IPF compared with controls (40.4% versus 22.4%, OR 2.35, p=0.008) and was associated with higher iron-dependent oxygen radical generation (HFE variant 107.4±56.0, HFE wild type (wt) 59.4±36.4 and controls 16.7±11.8 fluorescence units per 10(5) BAL cells; p=0.028 HFE variant versus HFE wt, p=0.006 HFE wt versus controls). The data suggest iron dysregulation associated with HFE allelic variants may play an important role in increasing susceptibility to environmental exposures, leading to recurring injury and fibrosis in IPF. Copyright ©ERS 2015.

  19. Oxygen activation at the plasma membrane: relation between superoxide and hydroxyl radical production by isolated membranes.

    Science.gov (United States)

    Heyno, Eiri; Mary, Véronique; Schopfer, Peter; Krieger-Liszkay, Anja

    2011-07-01

    Production of reactive oxygen species (hydroxyl radicals, superoxide radicals and hydrogen peroxide) was studied using EPR spin-trapping techniques and specific dyes in isolated plasma membranes from the growing and the non-growing zones of hypocotyls and roots of etiolated soybean seedlings as well as coleoptiles and roots of etiolated maize seedlings. NAD(P)H mediated the production of superoxide in all plasma membrane samples. Hydroxyl radicals were only produced by the membranes of the hypocotyl growing zone when a Fenton catalyst (FeEDTA) was present. By contrast, in membranes from other parts of the seedlings a low rate of spontaneous hydroxyl radical formation was observed due to the presence of small amounts of tightly bound peroxidase. It is concluded that apoplastic hydroxyl radical generation depends fully, or for the most part, on peroxidase localized in the cell wall. In soybean plasma membranes from the growing zone of the hypocotyl pharmacological tests showed that the superoxide production could potentially be attributed to the action of at least two enzymes, an NADPH oxidase and, in the presence of menadione, a quinone reductase.

  20. Atom interaction propensities of oxygenated chemical functions in crystal packings

    Directory of Open Access Journals (Sweden)

    Christian Jelsch

    2017-03-01

    Full Text Available The crystal contacts of several families of hydrocarbon compounds substituted with one or several types of oxygenated chemical groups were analyzed statistically using the Hirshfeld surface methodology. The propensity of contacts to occur between two chemical types is described with the contact enrichment descriptor. The systematic large enrichment ratios of some interactions like the O—H...O hydrogen bonds suggests that these contacts are a driving force in the crystal packing formation. The same statement holds for the weaker C—H...O hydrogen bonds in ethers, esters and ketones, in the absence of polar H atoms. The over-represented contacts in crystals of oxygenated hydrocarbons are generally of two types: electrostatic attractions (hydrogen bonds and hydrophobic interactions. While Cl...O interactions are generally avoided, in a minority of chloro-oxygenated hydrocarbons, significant halogen bonding does occur. General tendencies can often be derived for many contact types, but outlier compounds are instructive as they display peculiar or rare features. The methodology also allows the detection of outliers which can be structures with errors. For instance, a significant number of hydroxylated molecules displaying over-represented non-favorable oxygen–oxygen contacts turned out to have wrongly oriented hydroxyl groups. Beyond crystal packings with a single molecule in the asymmetric unit, the behavior of water in monohydrate compounds and of crystals with Z′ = 2 (dimers are also investigated. It was found in several cases that, in the presence of several oxygenated chemical groups, cross-interactions between different chemical groups (e.g. water/alcohols; alcohols/phenols are often favored in the crystal packings. While some trends in accordance with common chemical principles are retrieved, some unexpected results can however appear. For example, in crystals of alcohol–phenol compounds, the strong O—H...O hydrogen bonds between

  1. Characterization of atomic oxygen from an ECR plasma source

    International Nuclear Information System (INIS)

    Naddaf, M; Bhoraskar, V N; Mandale, A B; Sainkar, S R; Bhoraskar, S V

    2002-01-01

    A low-power microwave-assisted electron cyclotron resonance (ECR) plasma system is shown to be a powerful and effective source of atomic oxygen (AO) useful in material processing. A 2.45 GHz microwave source with maximum power of 600 W was launched into the cavity to generate the ECR plasma. A catalytic nickel probe was used to determine the density of AO. The density of AO is studied as a function of pressure and axial position of the probe in the plasma chamber. It was found to vary from ∼1x10 20 to ∼10x10 20 atom m -3 as the plasma pressure was varied from 0.8 to 10 mTorr. The effect of AO in oxidation of silver is investigated by gravimetric analysis. The stoichiometric properties of the oxide are studied using the x-ray photoelectron spectroscopy as well as energy dispersive x-ray analysis. The degradation of the silver surface due to sputtering effect was viewed by scanning electron spectroscopy. The sputtering yield of oxygen ions in the plasma is calculated using the TRIM code. The effects of plasma pressure and the distance from the ECR zone on the AO density were also investigated. The density of AO measured by oxidation of silver is in good agreement with results obtained from the catalytic nickel probe

  2. Characterization of atomic oxygen from an ECR plasma source

    Science.gov (United States)

    Naddaf, M.; Bhoraskar, V. N.; Mandale, A. B.; Sainkar, S. R.; Bhoraskar, S. V.

    2002-11-01

    A low-power microwave-assisted electron cyclotron resonance (ECR) plasma system is shown to be a powerful and effective source of atomic oxygen (AO) useful in material processing. A 2.45 GHz microwave source with maximum power of 600 W was launched into the cavity to generate the ECR plasma. A catalytic nickel probe was used to determine the density of AO. The density of AO is studied as a function of pressure and axial position of the probe in the plasma chamber. It was found to vary from ~1×1020 to ~10×1020 atom m-3 as the plasma pressure was varied from 0.8 to 10 mTorr. The effect of AO in oxidation of silver is investigated by gravimetric analysis. The stoichiometric properties of the oxide are studied using the x-ray photoelectron spectroscopy as well as energy dispersive x-ray analysis. The degradation of the silver surface due to sputtering effect was viewed by scanning electron spectroscopy. The sputtering yield of oxygen ions in the plasma is calculated using the TRIM code. The effects of plasma pressure and the distance from the ECR zone on the AO density were also investigated. The density of AO measured by oxidation of silver is in good agreement with results obtained from the catalytic nickel probe.

  3. Characterization of atomic oxygen from an ECR plasma source

    Energy Technology Data Exchange (ETDEWEB)

    Naddaf, M [Center for Advanced Studies in Material Science and Solid State Physics, University of Pune, Pune 411 007 (India); Bhoraskar, V N [Center for Advanced Studies in Material Science and Solid State Physics, University of Pune, Pune 411 007 (India); Mandale, A B [National Chemical Laboratory, Pashan, Pune 411008 (India); Sainkar, S R [National Chemical Laboratory, Pashan, Pune 411008 (India); Bhoraskar, S V [Center for Advanced Studies in Material Science and Solid State Physics, University of Pune, Pune 411 007 (India)

    2002-11-01

    A low-power microwave-assisted electron cyclotron resonance (ECR) plasma system is shown to be a powerful and effective source of atomic oxygen (AO) useful in material processing. A 2.45 GHz microwave source with maximum power of 600 W was launched into the cavity to generate the ECR plasma. A catalytic nickel probe was used to determine the density of AO. The density of AO is studied as a function of pressure and axial position of the probe in the plasma chamber. It was found to vary from {approx}1x10{sup 20} to {approx}10x10{sup 20} atom m{sup -3} as the plasma pressure was varied from 0.8 to 10 mTorr. The effect of AO in oxidation of silver is investigated by gravimetric analysis. The stoichiometric properties of the oxide are studied using the x-ray photoelectron spectroscopy as well as energy dispersive x-ray analysis. The degradation of the silver surface due to sputtering effect was viewed by scanning electron spectroscopy. The sputtering yield of oxygen ions in the plasma is calculated using the TRIM code. The effects of plasma pressure and the distance from the ECR zone on the AO density were also investigated. The density of AO measured by oxidation of silver is in good agreement with results obtained from the catalytic nickel probe.

  4. MISSE 6 Stressed Polymers Experiment Atomic Oxygen Erosion Data

    Science.gov (United States)

    deGroh, Kim K.; Banks, Bruce A.; Mitchell, Gianna G.; Yi, Grace T.; Guo, Aobo; Ashmeade, Claire C.; Roberts, Lily M.; McCarthy, Catherine E.; Sechkar, Edward A.

    2013-01-01

    Polymers and other oxidizable materials used on the exterior of spacecraft in the low Earth orbit (LEO) space environment can be eroded away by reaction with atomic oxygen (AO). For spacecraft design, it is important to know the LEO AO erosion yield, Ey (volume loss per incident oxygen atom), of materials susceptible to AO erosion. The Stressed Polymers Experiment was developed and flown as part of the Materials International Space Station Experiment 6 (MISSE 6) to compare the AO erosion yields of stressed and non-stressed polymers to determine if erosion is dependent upon stress while in LEO. The experiment contained 36 thin film polymer samples that were exposed to ram AO for 1.45 years. This paper provides an overview of the Stressed Polymers Experiment with details on the polymers flown, the characterization techniques used, the AO fluence, and the erosion yield results. The MISSE 6 data are compared to data for similar samples flown on previous MISSE missions to determine fluence or solar radiation effects on erosion yield.

  5. Radical zinc-atom-transfer-based carbozincation of haloalkynes with dialkylzincs

    Directory of Open Access Journals (Sweden)

    Fabrice Chemla

    2013-02-01

    Full Text Available The formation of alkylidenezinc carbenoids by 1,4-addition/carbozincation of dialkylzincs or alkyl iodides based on zinc atom radical transfer, in the presence of dimethylzinc with β-(propargyloxyenoates having pendant iodo- and bromoalkynes, is disclosed. Formation of the carbenoid intermediate is fully stereoselective at −30 °C and arises from a formal anti-selective carbozincation reaction. Upon warming, the zinc carbenoid is stereochemically labile and isomerizes to its more stable form.

  6. Improved simplified scheme of atom equivalents to calculate enthalpies of formation of alkyl radicals

    International Nuclear Information System (INIS)

    Castro, Eduardo A.

    2002-01-01

    An improved simplified method of atom equivalents is applied to the calculation of enthalpies of formation of several alkyl radicals. Some statistical mechanics and thermodynamic corrections are added to compare theoretical values with available experimental data. The estimation is quite satisfactory and the average error is similar to current experimental uncertainties, thus providing a direct and simple procedure for this sort of calculation when experimental results are unavailable or/and as an independent check when experimental data are in doubt. (Author) [es

  7. Studies on atom transfer radical polymerization of acrylates and styrenes with controlled polymeric block structures

    OpenAIRE

    Ibrahim, Khalid

    2006-01-01

    Atom transfer radical polymerization (ATRP) was applied to homo and block copolymerization of vinyl monomers methacrylates, acrylates, and styrene with iron (FeCl2.4H2O) as the transition metal in most cases. As complexing ligand either a commercially available ligand (triphenyl phosphine) (PPh3) or synthetic aliphatic amines were used. As initiators, methyl 2-bromopropionate, ethyl 2-bromoisobutyrate, α,α-dichloroacetophenone, and poly(ethylene oxide) macroinitiator were employed. Block ...

  8. PHOTOGENERATION OF SINGLET OXYGEN AND FREE RADICALS IN DISSOLVED ORGANIC MATTER ISOLATED FROM THE MISSISSIPPI AND ATCHAFALAYA RIVER PLUMES

    Science.gov (United States)

    The photoreactivity to UV light of ultrafiltered dissolved organic matter (DOM) collected during cruises along salinity transects in the Mississippi and Atchafalaya River plumes was examined by measuring photogenerated free radicals and singlet molecular oxygen (1O2) photosensiti...

  9. Generation of Oxygen Free Radicals by Proflavine: Implication in Protein Degradation

    Directory of Open Access Journals (Sweden)

    Mansour K.M. Gatasheh

    2017-07-01

    Full Text Available Proflavine, an acridine dye, is a known DNA intercalating agent. In the present study, we show that proflavine alone on photoillumination can generate reactive oxygen species (ROS. These proflavine-derived ROS cause damage to proteins, and this effect is enhanced when the divalent metal ion Cu (II is included in the reaction. Bathocuproine, a specific Cu (I sequestering agent, when present in the reaction mixture containing Cu (II, was found to inhibit the protein degradation, showing that Cu (I is an essential intermediate in the reaction. The effect of several scavengers of ROS such as superoxide dismutase, sodium azide, potassium iodide, and thiourea were examined on the protein damaging reaction. Potassium iodide was found to be the most effective in inhibiting protein damage followed by sodium azide and thiourea. Our results indicate the involvement of superoxide, singlet oxygen, triplet oxygen, and hydroxyl radicals in proflavine-induced damage to proteins.

  10. Role of macrophages and oxygen radicals in IgA induced lung injury in the rat

    International Nuclear Information System (INIS)

    Johnson, K.J.; Ward, P.A.; Kunkel, R.G.; Wilson, B.S.

    1986-01-01

    Acute lung injury in the rat has been induced by the instillation of affinity-purified mouse monoclonal IgA antibody with specific reactivity to dinitrophenol (DNP) coupled to albumin. This model of lung injury requires an intact complement system but not neutrophils, and evidence suggests that pulmonary macrophages are the critical effector cell. Macrophages retrievable from the lungs of the IgA immune complex treated rats are considerably increased in number as compared to control animals which received only the antibody. In addition these cells show evidence of activation in vivo with greater spontaneous generation of the superoxide anion (O 2 - ) as well as significantly enhanced O 2 - response in the presence of a second stimulus. Inhibition studies in vivo suggest that the lung injury is mediated by oxygen radical generation by the pulmonary macrophages. Pretreatment of rats with superoxide dismutase (SOD), catalase, the iron chelator deferoxamine or the hydroxyl radical scavenger dimethyl sulfoxide (DMSO) all markedly suppressed the development of the lung injury. In summary, these studies suggest that IgA immune complex injury in the rat lung is mediated by oxygen radical formation from pulmonary macrophages

  11. Numerical simulation of physicochemical interactions between oxygen atom and phosphatidylcholine due to direct irradiation of atmospheric pressure nonequilibrium plasma to biological membrane with quantum mechanical molecular dynamics

    Science.gov (United States)

    Uchida, Satoshi; Yoshida, Taketo; Tochikubo, Fumiyoshi

    2017-10-01

    Plasma medicine is one of the most attractive applications using atmospheric pressure nonequilibrium plasma. With respect to direct contact of the discharge plasma with a biological membrane, reactive oxygen species play an important role in induction of medical effects. However, complicated interactions between the plasma radicals and membrane have not been understood well. In the present work, we simulated elemental processes at the first stage of physicochemical interactions between oxygen atom and phosphatidylcholine using the quantum mechanical molecular dynamics code in a general software AMBER. The change in the above processes was classified according to the incident energy of oxygen atom. At an energy of 1 eV, the abstraction of a hydrogen atom and recombination to phosphatidylcholine were simultaneously occurred in chemical attachment of incident oxygen atom. The exothermal energy of the reaction was about 80% of estimated one based on the bond energies of ethane. An oxygen atom over 10 eV separated phosphatidylcholine partially. The behaviour became increasingly similar to physical sputtering. The reaction probability of oxygen atom was remarkably high in comparison with that of hydrogen peroxide. These results suggest that we can uniformly estimate various physicochemical dynamics of reactive oxygen species against membrane lipids.

  12. ATOM TRANSFER RADICAL POLYMERIZATION OF N-BUTYL METHACRYLATE IN AQUEOUS DISPERSED SYSTEMS: A MINIEMULSION APPROACH. (R826735)

    Science.gov (United States)

    Ultrasonication was applied in combination with a hydrophobe for the copper-mediated atom transfer radical polymerization of n-butyl methacrylate in an aqueous dispersed system. A controlled polymerization was successfully achieved, as demonstrated by a linear correlation between...

  13. Perhydropolysilazane derived silica coating protecting Kapton from atomic oxygen attack

    Energy Technology Data Exchange (ETDEWEB)

    Hu Longfei [China Academy of Aerospace Aerodynamics, Beijing 100074 (China); Li Meishuan, E-mail: mshli@imr.ac.cn [Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016 (China); Xu Caihong; Luo Yongming [Institute of Chemistry, Chinese Academy of Sciences, Beijing 100080 (China)

    2011-11-30

    By using surface sol-gel method with perhydropolysilazane (PHPS) as a precursor, a silica coating was prepared on a Kapton substrate as an atomic oxygen (AO) protective coating. The AO exposure tests were conducted in a ground-based simulator. It is found that the erosion yield of Kapton decreases by about three orders of magnitude after the superficial application of the coating. After AO exposure, the surface of the coating is smooth and uniform, no surface shrinkage induced cracks or undercutting erosion are observed. This is because that during AO exposure the PHPS is oxidized directly to form SiO{sub 2} without through intermediate reaction processes, the surface shrinkage and cracking tendency are prohibited. Meanwhile, this PHPS derived silica coating also presents self-healing effect due to the oxidation of free Si. Compared with other kinds of silica or organic polymer coatings, this PHPS derived silica coating exhibits a superior AO erosion resistance.

  14. Perhydropolysilazane derived silica coating protecting Kapton from atomic oxygen attack

    International Nuclear Information System (INIS)

    Hu Longfei; Li Meishuan; Xu Caihong; Luo Yongming

    2011-01-01

    By using surface sol–gel method with perhydropolysilazane (PHPS) as a precursor, a silica coating was prepared on a Kapton substrate as an atomic oxygen (AO) protective coating. The AO exposure tests were conducted in a ground-based simulator. It is found that the erosion yield of Kapton decreases by about three orders of magnitude after the superficial application of the coating. After AO exposure, the surface of the coating is smooth and uniform, no surface shrinkage induced cracks or undercutting erosion are observed. This is because that during AO exposure the PHPS is oxidized directly to form SiO 2 without through intermediate reaction processes, the surface shrinkage and cracking tendency are prohibited. Meanwhile, this PHPS derived silica coating also presents self-healing effect due to the oxidation of free Si. Compared with other kinds of silica or organic polymer coatings, this PHPS derived silica coating exhibits a superior AO erosion resistance.

  15. Atomic Oxygen Energy in Low Frequency Hyperthermal Plasma Ashers

    Science.gov (United States)

    Banks, Bruce A.; Miller, Sharon K R.; Kneubel, Christian A.

    2014-01-01

    Experimental and analytical analysis of the atomic oxygen erosion of pyrolytic graphite as well as Monte Carlo computational modeling of the erosion of Kapton H (DuPont, Wilmington, DE) polyimide was performed to determine the hyperthermal energy of low frequency (30 to 35 kHz) plasma ashers operating on air. It was concluded that hyperthermal energies in the range of 0.3 to 0.9 eV are produced in the low frequency air plasmas which results in texturing similar to that in low Earth orbit (LEO). Monte Carlo computational modeling also indicated that such low energy directed ions are fully capable of producing the experimentally observed textured surfaces in low frequency plasmas.

  16. Thermal relaxation of molecular oxygen in collisions with nitrogen atoms

    Energy Technology Data Exchange (ETDEWEB)

    Andrienko, Daniil A., E-mail: daniila@umich.edu; Boyd, Iain D. [Department of Aerospace Engineering, University of Michigan, 1320 Beal Ave., Ann Arbor, Michigan 48108 (United States)

    2016-07-07

    Investigation of O{sub 2}–N collisions is performed by means of the quasi-classical trajectory method on the two lowest ab initio potential energy surfaces at temperatures relevant to hypersonic flows. A complete set of bound–bound and bound–free transition rates is obtained for each precollisional rovibrational state. Special attention is paid to the vibrational and rotational relaxations of oxygen as a result of chemically non-reactive interaction with nitrogen atoms. The vibrational relaxation of oxygen partially occurs via the formation of an intermediate NO{sub 2} complex. The efficient energy randomization results in rapid vibrational relaxation at low temperatures, compared to other molecular systems with a purely repulsive potential. The vibrational relaxation time, computed by means of master equation studies, is nearly an order of magnitude lower than the relaxation time in N{sub 2}–O collisions. The rotational nonequilibrium starts to play a significant effect at translational temperatures above 8000 K. The present work provides convenient relations for the vibrational and rotational relaxation times as well as for the quasi-steady dissociation rate coefficient and thus fills a gap in data due to a lack of experimental measurements for this system.

  17. Effects of atomic oxygen on titanium dioxide thin film

    Science.gov (United States)

    Shimosako, Naoki; Hara, Yukihiro; Shimazaki, Kazunori; Miyazaki, Eiji; Sakama, Hiroshi

    2018-05-01

    In low earth orbit (LEO), atomic oxygen (AO) has shown to cause degradation of organic materials used in spacecrafts. Similar to other metal oxides such as SiO2, Al2O3 and ITO, TiO2 has potential to protect organic materials. In this study, the anatese-type TiO2 thin films were fabricated by a sol-gel method and irradiated with AO. The properties of TiO2 were compared using mass change, scanning electron microscope (SEM), atomic force microscope (AFM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), transmittance spectra and photocatalytic activity before and after AO irradiation. The results indicate that TiO2 film was hardly eroded and resistant against AO degradation. AO was shown to affects only the surface of a TiO2 film and not the bulk. Upon AO irradiation, the TiO2 films were slightly oxidized. However, these changes were very small. Photocatalytic activity of TiO2 was still maintained in spite of slight decrease upon AO irradiation, which demonstrated that TiO2 thin films are promising for elimination of contaminations outgassed from a spacecraft's materials.

  18. Reactions of atomic oxygen with the chlorate ion and the perchlorate ion

    Science.gov (United States)

    Anan'ev, Vladimir; Miklin, Mikhail; Kriger, Ludmila

    2014-06-01

    The reactions of the chlorate ion with atomic oxygen formed under photolysis of the nitrate ion introduced to potassium chlorate crystal by co-crystallization were studied by optical and infrared absorption spectroscopy. The perchlorate ion was found to form in solids as product of addition reaction of singlet atomic oxygen, formed under dissociation of the peroxynitrite ion - the product of isomerization of the excited nitrate ion. Triplet atomic oxygen does not react with the chlorate ion. The atomic oxygen formed under photolysis of the nitrate ion introduced to potassium perchlorate crystal by co-crystallization does not react with the perchlorate ion.

  19. Density functional theory study the effects of oxygen-containing functional groups on oxygen molecules and oxygen atoms adsorbed on carbonaceous materials.

    Science.gov (United States)

    Qi, Xuejun; Song, Wenwu; Shi, Jianwei

    2017-01-01

    Density functional theory was used to study the effects of different types of oxygen-containing functional groups on the adsorption of oxygen molecules and single active oxygen atoms on carbonaceous materials. During gasification or combustion reactions of carbonaceous materials, oxygen-containing functional groups such as hydroxyl(-OH), carbonyl(-CO), quinone(-O), and carboxyl(-COOH) are often present on the edge of graphite and can affect graphite's chemical properties. When oxygen-containing functional groups appear on a graphite surface, the oxygen molecules are strongly adsorbed onto the surface to form a four-member ring structure. At the same time, the O-O bond is greatly weakened and easily broken. The adsorption energy value indicates that the adsorption of oxygen molecules changes from physisorption to chemisorption for oxygen-containing functional groups on the edge of a graphite surface. In addition, our results indicate that the adsorption energy depends on the type of oxygen-containing functional group. When a single active oxygen atom is adsorbed on the bridge site of graphite, it gives rise to a stable epoxy structure. Epoxy can cause deformation of the graphite lattice due to the transition of graphite from sp2 to sp3 after the addition of an oxygen atom. For quinone group on the edge of graphite, oxygen atoms react with carbon atoms to form the precursor of CO2. Similarly, the single active oxygen atoms of carbonyl groups can interact with edge carbon atoms to form the precursor of CO2. The results show that oxygen-containing functional groups on graphite surfaces enhance the activity of graphite, which promotes adsorption on the graphite surface.

  20. N-Chlorosuccinimide (NCS): A Novel Initiator for Atom Transfer Radical Polymerization of Methyl Methacrylate

    Institute of Scientific and Technical Information of China (English)

    WANG,Xia-Yan; CHANG,Li-Qun; ZHOU,Hong; ZHANG,Ke-Da

    2006-01-01

    Atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) was achieved, using N-chlorosuccinimide (NCS) as an initiator together with catalytic system CuCl/PMDETA (N,N,N',N',N"-pentamethyldiethyl-enetriamine), CuCl/MA5-DETA (N,N,N',N',N"-penta(methylacrylate)diethylenetriamine), and CuCl/bipy (bipy=2,2'-bipyridyl) respectively. The results indicated that the polymerization possessed typical controlled/living radical polymerization characteristics. The analysis for terminal group of obtained polymer by 1H NMR proved that NCS is an initiator for ATRP. In comparison with NBS, the polymerization rate was slower and the resulted polymer had narrower molecular weight distribution (MWD) when NCS was employed as the initiator.

  1. Hydrophilization of poly(ether ether ketone) films by surface-initiated atom transfer radical polymerization

    DEFF Research Database (Denmark)

    Fristrup, Charlotte Juel; Jankova Atanasova, Katja; Hvilsted, Søren

    2010-01-01

    Surface-Initiated Atom Transfer Radical Polymerization (SI-ATRP) has been exploited to hydrophilize PEEK. The ketone groups on the PEEK surface were reduced to hydroxyl groups which were converted to bromoisobutyrate initiating sites for SI-ATRP. The modification steps were followed by contact...... angle measurements and XPS. Moreover, ATR FTIR has been used to confirm the formation of initiating groups. Grafting of PEGMA from PEEK was performed in aqueous solution. The presence of the PPEGMA grafts on PEEK was revealed by the thermograms from TGA whereas investigations with AFM rejected changes...

  2. Proton-Conducting Sulfonated Ionomers by Chemical Modification and Atom Transfer Radical Polymerization

    DEFF Research Database (Denmark)

    Nielsen, Mads Møller

    The cornerstone in this dissertation is made up by three individual assessments of the diversity in the macromolecular landscape that can be obtained by applying relatively few efficient chemical tools. The intention is to gain deeper knowledge on the chemical tuning of proton exchange membranes...... of hydrocarbon macromolecular architectures, PSU with postsulfonated polystyrene (PS) grafts are investigated. Here, IEC is controlled through the degree of substitution, the graft length and DS. The grafting is performed with atom transfer radical polymerization (ATRP). The third assessment is dedicated...... of control by ATRP and click chemistry enables a wide selection of polymer structures with the handles: degree of substitution (DS), polymerization and sulfonation, and blending....

  3. Modification of Jute Fibers with Polystyrene via Atom Transfer Radical Polymerization

    DEFF Research Database (Denmark)

    Plackett, David; Jankova, Katja Atanassova; Egsgaard, Helge

    2005-01-01

    Atom transfer radical polymerization (ATRP) was investigated as a method of covalently bonding polystyrene to jute (Corchorus capsularis) and as a possible approach to fiber composites with enhanced properties. Jute fibers were modified with a brominated initiator and subsequently ATRP modified...... to attach polystyrene and then examined using SEM, DSC, TGA, FTIR, XPS, elemental analysis, and Py-GC-MS. These techniques confirmed that polystyrene had been covalently bound to the fibers and consequently ATRP-modified jute fiber mats were used to prepare hot-pressed polystyrene composites. Composite...

  4. In situ AFM investigation of electrochemically induced surface-initiated atom-transfer radical polymerization.

    Science.gov (United States)

    Li, Bin; Yu, Bo; Zhou, Feng

    2013-02-12

    Electrochemically induced surface-initiated atom-transfer radical polymerization is traced by in situ AFM technology for the first time, which allows visualization of the polymer growth process. It affords a fundamental insight into the surface morphology and growth mechanism simultaneously. Using this technique, the polymerization kinetics of two model monomers were studied, namely the anionic 3-sulfopropyl methacrylate potassium salt (SPMA) and the cationic 2-(metharyloyloxy)ethyltrimethylammonium chloride (METAC). The growth of METAC is significantly improved by screening the ammonium cations by the addition of ionic liquid electrolyte in aqueous solution. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Fabrication of Robust and Antifouling Superhydrophobic Surfaces via Surface-Initiated Atom Transfer Radical Polymerization.

    Science.gov (United States)

    Xue, Chao-Hua; Guo, Xiao-Jing; Ma, Jian-Zhong; Jia, Shun-Tian

    2015-04-22

    Superhydrophobic surfaces were fabricated via surface-initiated atom transfer radical polymerization of fluorinated methacrylates on poly(ethylene terephthalate) (PET) fabrics. The hydrophobicity of the PET fabric was systematically tunable by controlling the polymerization time. The obtained superhydrophobic fabrics showed excellent chemical robustness even after exposure to different chemicals, such as acid, base, salt, acetone, and toluene. Importantly, the fabrics maintained superhydrophobicity after 2500 abrasion cycles, 100 laundering cycles, and long time exposure to UV irradiation. Also, the surface of the superhydrophobic fabrics showed excellent antifouling properties.

  6. Relationship between oxygen free radicals, cytokines, cortisol and stress complications in patients with acute cerebrovascular disease

    International Nuclear Information System (INIS)

    Zhu Yingbin; Wang Bingjie; Li Yunchao

    2010-01-01

    Objective: To investigate the relationship between oxygen free radicals, cytokines, cortisol and stress complications in patients with acute cerebrovascular disease (ACVD). Methods: Serum levels of superoxide dismutases (SOD), malonaldehyde (MDA) (with biochemistry) interleukin-6 (IL-6), tumor necrosis factor (TNF-α) and cortisol (with RIA) were measured in 32 patients with acute cerebrovascular disease (ACVD) plus stress complications and 48 patients without stress complications as well as 36 controls. Results: Serum SOD contents in non-stressed group were higher than those in stressed group (P<0.05) but lower than those of the controls (P<0.05). However the levels of MDA, IL-6, TNF-α and cortisol were highest in the stressed group and lowest in the controls (all P<0.05). Conclusion: Oxygen free radicals, IL-6, TNF-α and cortisol were involved in stress complications in patients with ACVD. Monitoring the levels of serum SOD, MDA, IL-6, TNF-α and cortisol could be useful for predicting stress complications and evaluating the therapeutic effect. (authors)

  7. Oxygen radical detoxification enzymes in doxorubicin-sensitive and -resistant P388 murine leukemia cells

    International Nuclear Information System (INIS)

    Ramu, A.; Cohen, L.; Glaubiger, D.

    1984-01-01

    One of the proposed mechanisms for the cytotoxic effects of anthracycline compounds suggests that the effect is mediated through the formation of intracellular superoxide radicals. It is therefore possible that doxorubicin resistance is associated with increased intracellular enzyme capacity to convert these superoxide radicals to inactive metabolites. We have measured the relative activities of superoxide dismutase, glutathione peroxidase, and catalase in P388 mouse leukemia cells and in a doxorubicin-resistant subline. Since oxygen-reactive metabolites also play a role in mediating the cytotoxicity of ionizing radiation, the radiosensitivity of both cell lines was also studied. No significant differences in superoxide dismutase activity between these cell lines was observed, indicating that they have a similar capacity to convert superoxide anion radicals to hydrogen peroxide. P388 cells that are resistant to doxorubicin have 1.5 times the glutathione content and 1.5 times the activity of glutathione peroxidase measured in drug-sensitive P388 cells. However, incubation with 1-chloro-2,4-dinitrobenzene, which covalently binds glutathione, had no effect on the sensitivity of either cell line to doxorubicin. Measured catalase activity in drug-resistant P388 cells was one-third of the activity measured in doxorubicin-sensitive P388 cells. The activity of this enzyme was much higher than that of glutathione peroxidase in terms of H 2 O 2 deactivation in both cell lines. It is therefore unlikely that doxorubicin-resistant P388 cells have an increased ability to detoxify reactive oxygen metabolites when compared to drug-sensitive cells. Doxorubicin-resistant P388 cells were significantly more sensitive to X-irradiation than were drug-sensitive P388 cells. These observations suggest that the difference in catalase activity in these cell lines may be associated with the observed differences in radiosensitivity

  8. Kinetics of several oxygenated carbon-centered free radical reactions with NO2.

    Science.gov (United States)

    Rissanen, Matti P; Arppe, Suula L; Timonen, Raimo S

    2013-05-16

    Five oxygenated carbon-centered free radical reactions with nitrogen dioxide (NO2) have been studied in direct time-resolved measurements. Experiments were conducted in a temperature-controlled flow tube reactor coupled to a 193 nm exciplex laser photolysis and a resonance gas lamp photoionization mass spectrometer. Reactions were investigated under pseudofirst-order conditions, with the NO2 concentrations of the experiments in great excess over the initial radical concentrations ([R]0 CH3CO radical reactions with NO2 and, hence, includes the three smallest hydroxyalkyl radical species (CH2OH, CH2CH2OH, and CH3CHOH). The obtained rate coefficients are high with the temperature-dependent rate coefficients given by a formula k(T) = k300K × (T/300 K)(-n) as (in units of cm(3) molecule(-1) s(-1)): k(CH2OH + NO2) = (8.95 ± 2.70) × 10(-11) × (T/300 K)(-0.54±0.27) (T = 298-363 K), k(CH2CH2OH + NO2) = (5.99 ± 1.80) × 10(-11) × (T/300 K)(-1.49±0.45)(T = 241-363 K), k(CH3CHOH + NO2) = (7.48 ± 2.24) × 10(-11) × (T/300 K)(-1.36±0.41) (T = 266-363 K), k(CH3OCH2 + NO2) = (7.85 ± 2.36) × 10(-11) × (T/300 K)(-0.93±0.28) (T = 243-363 K), and k(CH3CO + NO2) = (2.87 ± 0.57) × 10(-11) × (T/300 K)(-2.45±0.49) (T = 241-363 K), where the uncertainties refer to the estimated overall uncertainties of the values obtained. The determined rate coefficients show negative temperature dependence with no apparent bath gas pressure dependence under the current experimental conditions (241-363 K and about 1-3 Torr helium). This behavior is typical for a radical-radical addition mechanism with no potential energy barrier above the energy of the separated reactants in the entrance channel of the reaction. Unfortunately the absence of detected product signals prevented gaining deeper insight into the reaction mechanism.

  9. Demonstration using EPR spin-trapping of an oxygen-dependent, carbon-centered free radical generated by soybean lipoxygenase

    International Nuclear Information System (INIS)

    Carpenter, M.F.; Smith, F.L.

    1986-01-01

    Purified prostaglandin synthase produces a carbon-centered, oxygen-dependent free radical which they have shown forms a spin-trapped adduct with 4-POBN and has characteristic hyperfine spin coupling constants (hfsc). As production of this radical is cyclooxygenase-dependent, additional studies on radical production were done using soybean lipoxygenase. The latter generates a lipid substrate-derived free radical trapped by the EPR spin trap 4-POBN [α-(4-pyridyl 1-oxide)N-tert-butyl nitrone]. With linoleate as substrate, the hfsc are a/sub N/ = 15.5 G, a/sub β//sup H/ = 2.7 G. This signal is inhibited by ETYA, various antioxidants and heat inactivation of the enzyme. Additional hfsc are not seen when the enzyme is incubated in an 17 O 2 atmosphere, but the signal is inhibited by anaerobeosis. Substitution of 13 C 18 carbon free fatty acids from Chlorella pyrenoisdosa for linoleate produces 2 new lines for each of the original 6 observed with 12 C substrate; the new spectrum has hfsc of a/sub N/ = 16.0 G, a/sub β//sup H/ = 2.4 G, a/sub β/ 13 C = 4.2 G. This demonstrates that the radical is carbon centered and oxygen-dependent and appears not to be the same radical formed by enzymic hydrogen abstraction from the lipid substrate. This radical and the prostaglandin synthase-dependent radical appear to be nearly identical

  10. Pressure broadening of atomic oxygen two-photon absorption laser induced fluorescence

    NARCIS (Netherlands)

    Marinov, D.; Drag, C.; Blondel, C.; Guaitella, O.; Golda, J.; Klarenaar, B.L.M.; Engeln, R.A.H.; Schulz-von der Gathen, V.; Booth, J.-P.

    2016-01-01

    Atomic oxygen, considered to be a determining reactant in plasma applications at ambient pressure, is routinely detected by two-photon absorption laser induced fluorescence (TALIF). Here, pressure broadening of the (2p 4 3 P 2  →  3p 3 P J=0,1,2) two-photon transition in oxygen atoms was

  11. UV Observations of Atomic Oxygen in the Cusp Region

    Science.gov (United States)

    Fritz, B.; Lessard, M.; Dymond, K.; Kenward, D. R.; Lynch, K. A.; Clemmons, J. H.; Hecht, J. H.; Hysell, D. L.; Crowley, G.

    2017-12-01

    The Rocket Experiment for Neutral Upwelling (RENU) 2 launched into the dayside cusp on 13 December, 2015. The sounding rocket payload carried a comprehensive suite of particle, field, and remote sensing instruments to characterize the thermosphere in a region where pockets of enhanced neutral density have been detected [Lühr et al, 2004]. An ultraviolet photomultiplier tube (UV PMT) was oriented to look along the magnetic field line and remotely detect neutral atomic oxygen (OI) above the payload. The UV PMT measured a clear enhancement as the payload descended through a poleward moving auroral form, an indicator of structure in both altitude and latitude. Context for the UV PMT measurement is provided by the Special Sensor Ultraviolet Imager (SSULI) instrument on the Defense Meteorological Space Program (DMSP) satellite, which also measured OI as it passed through the cusp. UV tomography of SSULI observations produces a two-dimensional cross-section of volumetric emission rates in the high-latitude thermosphere prior to the RENU 2 flight. The volume emission rate may then be inverted to produce a profile of neutral density in the thermosphere. A similar technique is used to interpret the UV PMT measurement and determine structure in the thermosphere as RENU 2 descended through the cusp.

  12. Functionalized polymer film surfaces via surface-initiated atom transfer radical polymerization

    International Nuclear Information System (INIS)

    Hu, Y.; Li, J.S.; Yang, W.T.; Xu, F.J.

    2013-01-01

    The ability to manipulate and control the surface properties of polymer films, without altering the substrate properties, is crucial to their wide-spread applications. In this work, a simple one-step method for the direct immobilization of benzyl chloride groups (as the effective atom transfer radical polymerization (ATRP) initiators) on the polymer films was developed via benzophenone-induced coupling of 4-vinylbenzyl chloride (VBC). Polyethylene (PE) and nylon films were selected as examples of polymer films to illustrate the functionalization of film surfaces via surface-initiated ATRP. Functional polymer brushes of (2-dimethylamino)ethyl methacrylate, sodium 4-styrenesulfonate, 2-hydroxyethyl methacrylate and glycidyl methacrylate, as well as their block copolymer brushes, have been prepared via surface-initiated ATRP from the VBC-coupled PE or nylon film surfaces. With the development of a simple approach to the covalent immobilization of ATRP initiators on polymer film surfaces and the inherent versatility of surface-initiated ATRP, the surface functionality of polymer films can be precisely tailored. - Highlights: ► Atom transfer radical polymerization initiators were simply immobilized. ► Different functional polymer brushes were readily prepared. ► Their block copolymer brushes were also readily prepared

  13. On the mechanism of activation of copper-catalyzed atom transfer radical polymerization

    International Nuclear Information System (INIS)

    Isse, Abdirisak Ahmed; Bortolamei, Nicola; De Paoli, Patrizia; Gennaro, Armando

    2013-01-01

    The mechanism of activation of atom transfer radical polymerization (ATRP) has been analyzed by investigating the kinetics of dissociative electron transfer (ET) to alkyl halides (RX) in acetonitrile. Using a series of alkyl halides, including both bromides and chlorides, the rate constants of ET (k ET ) to RX by electrogenerated aromatic radical anions (A· − ) acting as outer-sphere donors have been measured and analyzed according to the current theories of dissociative ET. This has shown that the kinetic data fit very well the “sticky” dissociative ET model with the formation of a weak adduct held together by electrostatic interactions. The rate constants of activation, k act , of some alkyl halides, namely chloroacetonitrile, methyl 2-bromopropionate and ethyl chloroacetate, by [Cu I L] + (L = tris(2-dimethylaminoethyl)amine, tris(2-pyridylmethyl)amine, 1,1,4,7,7-pentamethyldiethylenetriamine) have also been measured in the same experimental conditions. Comparisons of the measured k act values with those predicted assuming an outer-sphere ET for the complexes have shown that activation by Cu(I) is 7–10 orders of magnitude faster than required by outer-sphere ET. Therefore, the mechanism of RX activation by Cu(I) complexes used as catalysts in ATRP occurs by an inner-sphere ET or more appropriately by a halogen atom abstraction

  14. An Atmospheric Atomic Oxygen Source for Cleaning Smoke Damaged Art Objects

    Science.gov (United States)

    Banks, Bruce A.; Rutledge, Sharon K.; Norris, Mary Jo

    1998-01-01

    Soot and other carbonaceous combustion products deposited on the surfaces of porous ceramic, stone, ivory and paper can be difficult to remove and can have potentially unsatisfactory results using wet chemical and/or abrasive cleaning techniques. An atomic oxygen source which operates in air at atmospheric pressure, using a mixture of oxygen and helium, has been developed to produce an atomic oxygen beam which is highly effective in oxidizing soot deposited on surfaces by burning candles made of paraffin, oil or rendered animal fat. Atomic oxygen source operating conditions and the results of cleaning soot from paper, gesso, ivory, limestone and water color-painted limestone are presented,

  15. Role of oxygen free radicals in the proliferation of myofibroblasts induced by AngII

    Directory of Open Access Journals (Sweden)

    Liying Wang

    2013-02-01

    Full Text Available Previous studies have demonstrated the important role of angiotension II (AngII in promoting proliferation of myofibroblasts (myoFbs and myocardial fibrosis. However, the underlying mechanisms and the role of oxygen free radicals in the proliferation of myofibroblasts induced by AngII are unclear. The present study was designed to shed light on this issue through exploration of AngII signaling pathways via in vitro experiments. Primary cultures of neonatal rat myoFbs were divided into five groups which were treated with AngII (10−8 to 10−6 M, AngII with the antioxidant N-acetyl-L-cysteine (NAC, or normal culture medium. We observed the proliferation of myoFbs as induced by AngII at different concentrations with MTT. Reactive oxygen species (ROS levels in myoFbs were detected by monitoring the fluorescence of 2′,7′-dichlorofluorescein. The contents and levels of oxygen free radicals (OH· in the three groups were detected by spectrophotometer, immunocytochemical staining, and confocal fluorescence. Western blot and image analysis were used to measure membrane translocation and expression of phospho-protein kinase Cα. MyoFbs incubated with AngII (10−8 to 10−6 M for 24 h increased their rate of proliferation, the content of OH·, and expression of ROS (P<0.01 vs. control group, whereas these parameters decreased in the presence of NAC. Immunocytochemistry, confocal fluorescence staining and image analysis showed that AngII could promote the translocation and expression of p-PKCα in membrane, and the antioxidant NAC blocked this increase (P<0.01. Western blot results also showed that NAC could inhibit the expression of p-PKCα.

  16. The Materials Chemistry of Atomic Oxygen with Applications to Anisotropic Etching of Submicron Structures in Microelectronics and the Surface Chemistry Engineering of Porous Solids

    Science.gov (United States)

    Koontz, Steve L.; Leger, Lubert J.; Wu, Corina; Cross, Jon B.; Jurgensen, Charles W.

    1994-01-01

    Neutral atomic oxygen is the most abundant component of the ionospheric plasma in the low Earth orbit environment (LEO; 200 to 700 kilometers altitude) and can produce significant degradation of some spacecraft materials. In order to produce a more complete understanding of the materials chemistry of atomic oxygen, the chemistry and physics of O-atom interactions with materials were determined in three radically different environments: (1) The Space Shuttle cargo bay in low Earth orbit (the EOIM-3 space flight experiment), (2) a high-velocity neutral atom beam system (HVAB) at Los Alamos National Laboratory (LANL), and (3) a microwave-plasma flowing-discharge system at JSC. The Space Shuttle and the high velocity atom beam systems produce atom-surface collision energies ranging from 0.1 to 7 eV (hyperthermal atoms) under high-vacuum conditions, while the flowing discharge system produces a 0.065 eV surface collision energy at a total pressure of 2 Torr. Data obtained in the three different O-atom environments referred to above show that the rate of O-atom reaction with polymeric materials is strongly dependent on atom kinetic energy, obeying a reactive scattering law which suggests that atom kinetic energy is directly available for overcoming activation barriers in the reaction. General relationships between polymer reactivity with O atoms and polymer composition and molecular structure have been determined. In addition, vacuum ultraviolet photochemical effects have been shown to dominate the reaction of O atoms with fluorocarbon polymers. Finally, studies of the materials chemistry of O atoms have produced results which may be of interest to technologists outside the aerospace industry. Atomic oxygen 'spin-off' or 'dual use' technologies in the areas of anisotropic etching in microelectronic materials and device processing, as well as surface chemistry engineering of porous solid materials are described.

  17. Development of a Supersonic Atomic Oxygen Nozzle Beam Source for Crossed Beam Scattering Experiments

    Science.gov (United States)

    Sibener, S. J.; Buss, R. J.; Lee, Y. T.

    1978-05-01

    A high pressure, supersonic, radio frequency discharge nozzle beam source was developed for the production of intense beams of ground state oxygen atoms. An efficient impedance matching scheme was devised for coupling the radio frequency power to the plasma as a function of both gas pressure and composition. Techniques for localizing the discharge directly behind the orifice of a water-cooled quartz nozzle were also developed. The above combine to yield an atomic oxygen beam source which produces high molecular dissociation in oxygen seeded rare gas mixtures at total pressures up to 200 torr: 80 to 90% dissociation for oxygen/argon mixtures and 60 to 70% for oxygen/helium mixtures. Atomic oxygen intensities are found to be greater than 10{sup 17} atom sr{sup -1} sec{sup -1}. A brief discussion of the reaction dynamics of 0 + IC1 ..-->.. I0 + C1 is also presented.

  18. Influence of Atomic Oxygen Exposure on Friction Behavior of 321 Stainless Steel

    Science.gov (United States)

    Liu, Y.; Yang, J.; Ye, Z.; Dong, S.; Zhang, L.; Zhang, Z.

    Atomic oxygen (AO) exposure testing has been conducted on a 321 stainless steel rolled 1 mm thick sheet to simulate the effect of AO environment on steel in low Earth orbit (LEO). An atomic oxygen exposure facility was employed to carry out AO experiments with the fluence up to ~1021 atom/cm2. The AO exposed specimens were evaluated in air at room temperature using a nanoindenter and a tribological system. The exposed surfaces were analyzed usign XPS technique.

  19. Prevention of alloimmunization by ultraviolet-B irradiation. Inactivation of leukocytes and the generation of active oxygen and radicals

    International Nuclear Information System (INIS)

    Takahashi, Tsuneo; Mogi, Yuko; Sekiguchi, Sadayoshi; Akasaka, Junichi; Kamo, Naoki; Kuwabara, Mikinori.

    1994-01-01

    UV-B irradiation of platelet concentrates (PC) has been tried in several institutes to inactivate leukocytes in PC and prevent alloimmunization on platelet transfusion. However, the mechanism of inactivation of leukocytes contaminating PC has not been fully understood. It is known that UV-B light is absorbed by photosensitizers in cells and produces active oxygen and radicals, such as singlet oxygen, superioxide anions and hydroxyl radicals. These active oxygen or radicals should injure cellular components and this could cause the suppression of cellular functions. In this study, we investigated the relationships among UV-B irradiation, free radical generation and leukocyte inactivation. We found the evidence that active oxygen and radicals were produced in peripheral blood mononuclear cells by UV-B irradiation. UV-B irradiation suppressed the stimulatory function of leukocytes in a mixed lymphocyte reaction (MLR), and the suppression depended on the dosage of UV-B. Even a low dosage of UV-B, 10 J/m 2 , could inhibit the MLR if the irradiated cells were incubated at 37degC for 24 hours before co-culture with responder cells. Treatments of cells with the exogenous singlet oxygen or superoxide anions also caused suppression of the stimulatory function in the MLR, inhibition of capping formation of HLA-DR antigens, and an increase of intracellular free Ca 2+ levels as did the UV-B treatment. These results indicate that the active oxygen or radicals generated in UV-B-irradiated leukocytes could be one of the causes of leukocyte inactivation. (author0

  20. Physiology of free radicals

    Directory of Open Access Journals (Sweden)

    Stevanović Jelka

    2011-01-01

    Full Text Available Free radicals imply that every atom, molecule, ion, group of atoms, or molecules with one or several non-paired electrons in outer orbital. Among these are: nitrogenoxide (NO•, superoxide-anion-radical (O2•-, hydroxyl radical (OH•, peroxyl radical (ROO•, alcoxyl radical (RO• and hydroperoxyl radical (HO2•. However, reactive oxygen species also include components without non-paired electrons in outer orbital (so-called reactive non-radical agents, such as: singlet oxygen (1O2, peroxynitrite (ONOO-, hydrogen-peroxide (H2O2, hypochloric acid (eg. HOCl and ozone (O3. High concentrations of free radicals lead to the development of oxidative stress which is a precondition for numerous pathological effects. However, low and moderate concentrations of these matter, which occur quite normally during cell metabolic activity, play multiple significant roles in many reactions. Some of these are: regulation of signal pathways within the cell and between cells, the role of chemoattractors and leukocyte activators, the role in phagocytosis, participation in maintaining, changes in the position and shape of the cell, assisting the cell during adaption and recovery from damage (e.g.caused by physical effort, the role in normal cell growth, programmed cell death (apoptosis and cell ageing, in the synthesis of essential biological compounds and energy production, as well as the contribution to the regulation of the vascular tone, actually, tissue vascularization.

  1. 3D scaffolds from vertically aligned carbon nanotubes/poly(methyl methacrylate) composites via atom transfer radical polymerization

    Energy Technology Data Exchange (ETDEWEB)

    Tebikachew, Behabtu; Magina, Sandra [CICECO, Department of Chemistry, University of Aveiro (Portugal); Mata, Diogo; Oliveira, Filipe J.; Silva, Rui F. [CICECO, Department of Materials and Ceramic Engineering, University of Aveiro (Portugal); Barros-Timmons, Ana, E-mail: anabarros@ua.pt [CICECO, Department of Chemistry, University of Aveiro (Portugal)

    2015-01-15

    Vertically aligned carbon nanotubes (VACNTs) synthesized by Thermal Chemical Vapour Deposition (TCVD) were modified using an Ar:O{sub 2} (97:3) plasma to generate oxygen-containing functional groups on the surface for subsequent modification. X-ray photo-emission spectroscopy (XPS) and micro-Raman analyses confirmed the grafting of those functional groups onto the surface of the nanotubes as well as the removal of amorphous carbon produced and deposited on the VACNT forests during the CVD process. The plasma treated VACNT forests were further modified with 2-bromo-2-methylpropionyl bromide, an atom transfer radical polymerization (ATRP) initiator, to grow poly(methyl methacrylate) (PMMA) chains from the forests via ATRP. Scanning transmission electron microscopy (STEM) of the ensuing VACNT/PMMA composites confirmed the coating of the nanotube forests with the PMMA polymer. 3D scaffolds of polymeric composites with honeycomb like structure were then obtained. Compressive tests have shown that the VACNT/PMMA composite has higher compressive strength than the pristine forest. - Highlights: • Vertically aligned carbon nanotubes (VACNTs) were synthesized and plasma modified. • X-ray photo-emission and Raman spectroscopies confirmed the VACNTs modification. • Poly(methyl methacrylate) chains were grown via ATRP from the VACNTs. • STEM of the VACNT/PMMA composites confirmed that PMMA surrounds the nanotubes. • VACNT/PMMA composite has higher compressive strength compared to the pristine forest.

  2. 3D scaffolds from vertically aligned carbon nanotubes/poly(methyl methacrylate) composites via atom transfer radical polymerization

    International Nuclear Information System (INIS)

    Tebikachew, Behabtu; Magina, Sandra; Mata, Diogo; Oliveira, Filipe J.; Silva, Rui F.; Barros-Timmons, Ana

    2015-01-01

    Vertically aligned carbon nanotubes (VACNTs) synthesized by Thermal Chemical Vapour Deposition (TCVD) were modified using an Ar:O 2 (97:3) plasma to generate oxygen-containing functional groups on the surface for subsequent modification. X-ray photo-emission spectroscopy (XPS) and micro-Raman analyses confirmed the grafting of those functional groups onto the surface of the nanotubes as well as the removal of amorphous carbon produced and deposited on the VACNT forests during the CVD process. The plasma treated VACNT forests were further modified with 2-bromo-2-methylpropionyl bromide, an atom transfer radical polymerization (ATRP) initiator, to grow poly(methyl methacrylate) (PMMA) chains from the forests via ATRP. Scanning transmission electron microscopy (STEM) of the ensuing VACNT/PMMA composites confirmed the coating of the nanotube forests with the PMMA polymer. 3D scaffolds of polymeric composites with honeycomb like structure were then obtained. Compressive tests have shown that the VACNT/PMMA composite has higher compressive strength than the pristine forest. - Highlights: • Vertically aligned carbon nanotubes (VACNTs) were synthesized and plasma modified. • X-ray photo-emission and Raman spectroscopies confirmed the VACNTs modification. • Poly(methyl methacrylate) chains were grown via ATRP from the VACNTs. • STEM of the VACNT/PMMA composites confirmed that PMMA surrounds the nanotubes. • VACNT/PMMA composite has higher compressive strength compared to the pristine forest

  3. Preparation of poly(methyl methacrylate) grafted titanate nanotubes by in situ atom transfer radical polymerization

    International Nuclear Information System (INIS)

    Gao Yuan; Zhou Yongfeng; Yan Deyue; Gao Xueping

    2008-01-01

    This paper reports the successful preparation of core-shell hybrid nanocomposites by a 'grafting from' approach based on in situ atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) from titanate nanotubes (TNTs). Transmission electron microscope (TEM) images of the products provide direct evidence for the formation of a core-shell structure, possessing a hard core of TNTs and a soft shell of poly-MMA (PMMA). Fourier-transform infrared spectroscopy (FT-IR), hydrogen nuclear magnetic resonance ( 1 H NMR), scanning electron microscopy (SEM), and thermal gravimetric analysis (TGA) were used to determine the chemical structure, morphology, and the grafted PMMA quantities of the resulting products. The grafted PMMA content was well controlled and increased with increasing monomer/initiator ratio. Further copolymerization of hydroxyethyl methacrylate (HEMA) with PMMA-coated TNTs as initiators was realized, illustrating the 'living' characteristics of the ATRP method used in this paper.

  4. A New Initiator Cholesteryl Chloroformate for Cupper-Based Atom Transfer Radical Polymerization of Methyl Methacrylate

    Institute of Scientific and Technical Information of China (English)

    曹健; 楚娟; 张可达

    2004-01-01

    The polymerization of metyl methacrylate (MMA) was studied in detail by use of CuCl/L as a catalyst and cholesteryl chloroformate (CC) as an initiator. It was found that the atom transfer radical polymerization of MMA could proceed when L equals to a multidentate aliphatic amine ligand, N,N,N',N",N"-penta(methyl acrylate)diethylenetriamine (MA5-DETA), and no polymerization was occurred while L=2,2'-bipyridine and 1,10-phenanthroline. The linear proportionality of the molecular weights to the conversions and straight lines observed in ln[M]0/[M] versus time plots indicated that the present polymerization system had the typical controlled polymerization characteristics.

  5. SYNTHESIS OF BLOCK COPOLYMER BY INTEGRATED LIVING ANIONIC POLYMERIZATION-ATOM TRANSFER RADICAL POLYMERIZATION (ATRP)

    Institute of Scientific and Technical Information of China (English)

    Bing Liu; Feng Liu; Ning Luo; Sheng-kang Ying; Qing Liu

    2000-01-01

    Alpha-trichloroacetoxy terminated polystyrene oligomer (PS-CH2CH2OCOCCl3) and poly-(styrene-b-butadiene)oligomer [P(S-b-B)-CH2CH2OCOCCl3)] were synthesized by living anionic polymeri-zation using n-butyllithium as initiator.Then the PS-CH2CH2OCOCCl3 (PS-Cl3) or P(S-b-B)-CH2CH2O-COCCl3 (PSB-Cl3) was used as the macroinitiator in the polymerization of (meth)acrylates in the presence of CuX/bpy. AB diblock and ABC triblock copolymers were prepared by the integrated living anionic polymerization (LAP)-atom transfer radical polymerization (ATRP). The structures of the PSB-Cl3 and the P(S-b-MMA) were identified by FTIR and 1H-NMR spectrum, respectively. A new way to design block copolymers (the combination of LAP and ATRP) was developed.

  6. PREPARATION AND PROPERTIES OF MMA/1-PROPYLMETHACRYLATE-POSS COPOLYMER WITH ATOM TRANSFER RADICAL POLYMERIZATION

    Institute of Scientific and Technical Information of China (English)

    He-xin Zhang; Ho-young Lee; Young-jun Shin; Dong-ho Lee; Seok Kyun Noh

    2008-01-01

    The methyl methacrylate(MMA)/1-propylmethacrylate-polyhedral oligomeric silsesquioxane(PM-POSS) copolymers were synthesized via atom transfer radical polymerization with CuBr as catalyst.The unreacted PM-POSS monomer could be removed completely by washing the copolymerization product with n-hexane.The copolymers were characterized with 1H-NMR,X-ray diffraction,difierential scanning calorimetry,thermogravimetric analysis and gel permeatlon chromatography.With increasing PM-POSS feed ratio.the total conversion increased while the glass transition temperatures of copolymer decreased.The thermogravimetric analysis demonstrated that the thermal stability of copolymer improved slightly with PM-POSS addition.The molecular weight of copolymers increased with incorporation of PM-POSS.

  7. Three Arm Star Homo- And Co-Polymers Via Atom Transfer Radical Polymerization

    International Nuclear Information System (INIS)

    Amin, A.; Sobh, R.A.; Ayoub, M.M.H.

    2005-01-01

    Star homo and co-polymers of some vinyl monomers such as methylmethacrylate, butylmethacrylate and styrene (MMA, BMA, St.) were prepared using N, N, N', N' tetramethylethylenediamine ligand/ CuBr catalytic system via atom transfer radical polymerization (ATRP). Three armed benzene based core was successfully used as initiator. Low polydispersities and regular molecular weight values were obtained in most cases especially at low conversions. MMA and BuMA showed comparable behavior where controlled and true ATRP was observed even at the high conversions. However, styrene monomer recorded irregular high polydispersities at high conversions in spite of the relatively low molecular weight values. 1HNMR confirmed the structures of the resulting polymers. Transmission Electron microscope (TEM) proved the nano-structure of the star polymers. The thermal behavior of the MMA star homo and copolymers was studied. The effect of the star shape on the thermal behavior was very clear with respect to the linear ones

  8. Kinetics of Several Oxygen-Containing Carbon-Centered Free Radical Reactions with Nitric Oxide.

    Science.gov (United States)

    Rissanen, Matti P; Ihlenborg, Marvin; Pekkanen, Timo T; Timonen, Raimo S

    2015-07-16

    Kinetics of four carbon-centered, oxygen-containing free radical reactions with nitric oxide (NO) were investigated as a function of temperature at a few Torr pressure of helium, employing flow tube reactors coupled to a laser-photolysis/resonance-gas-discharge-lamp photoionization mass spectrometer (LP-RPIMS). Rate coefficients were directly determined from radical (R) decay signals under pseudo-first-order conditions ([R]0 ≪ [NO]). The obtained rate coefficients showed negative temperature dependences, typical for a radical-radical association process, and can be represented by the following parametrizations (all in units of cm(3) molecule(-1) s(-1)): k(CH2OH + NO) = (4.76 × 10(-21)) × (T/300 K)(15.92) × exp[50700/(RT)] (T = 266-363 K, p = 0.79-3.44 Torr); k(CH3CHOH + NO) = (1.27 × 10(-16)) × (T/300 K)(6.81) × exp[28700/(RT)] (T = 241-363 K, p = 0.52-3.43 Torr); k(CH3OCH2 + NO) = (3.58 ± 0.12) × 10(-12) × (T/300 K)(-3.17±0.14) (T = 221-363 K, p = 0.50-0.80 Torr); k(T)3 = 9.62 × 10(-11) × (T/300 K)(-5.99) × exp[-7100/(RT)] (T = 221-473 K, p = 1.41-2.95 Torr), with the uncertainties given as standard errors of the fits and the overall uncertainties estimated as ±20%. The rate of CH3OCH2 + NO reaction was measured in two density ranges due to its observed considerable pressure dependence, which was not found in the studied hydroxyalkyl reactions. In addition, the CH3CO + NO rate coefficient was determined at two temperatures resulting in k298K(CH3CO + NO) = (5.6 ± 2.8) × 10(-13) cm(3) molecule(-1) s(-1). No products were found during these experiments, reasons for which are briefly discussed.

  9. Vibrational Relaxation of Ground-State Oxygen Molecules With Atomic Oxygen and Carbon Dioxide

    Science.gov (United States)

    Saran, D. V.; Pejakovic, D. A.; Copeland, R. A.

    2008-12-01

    Vertical water vapor profiles are key to understanding the composition and energy budget in the mesosphere and lower thermosphere (MLT). The SABER instrument onboard NASA's TIMED satellite measures such profiles by detecting H2O(ν2) emission in the 6.8 μm region. Collisional deactivation of vibrationally excited O2, O2(X3Σ-g, υ = 1) + H2O ↔ O2(X3Σ-g, υ = 0) + H2O(ν2), is an important source of H2O(ν2). A recent study has identified two other processes involving excited O2 that control H2O(ν2) population in the MLT: (1) the vibrational-translational (V-T) relaxation of O2(X3Σ-g, υ = 1) level by atomic oxygen and (2) the V-V exchange between CO2 and excited O2 molecules [1]. Over the past few years SRI researchers have measured the atomic oxygen removal process mentioned above at room temperature [2] and 240 K [3]. These measurements have been incorporated into the models for H2O(ν2) emission [1]. Here we report laboratory studies of the collisional removal of O2(X3Σ-g, υ = 1) by O(3P) at room temperature and below, reaching temperatures relevant to mesopause and polar summer MLT (~150 K). Instead of directly detecting the O2(X3Σ-g, υ = 1) population, a technically simpler approach is used in which the υ = 1 level of the O2(a1Δg) state is monitored. A two-laser method is employed, in which the pulsed output of the first laser near 285 nm photodissociates ozone to produce atomic oxygen and O2(a1Δg, υ = 1), and the pulsed output of the second laser detects O2(a1Δg, υ = 1) via resonance-enhanced multiphoton ionization. With ground-state O2 present, owing to the rapid equilibration of the O2(X3Σ-g, υ = 1) and O2(a1Δg, υ = 1) populations via the processes O2(a1Δg, υ = 1) + O2(X3Σ-g, υ = 0) ↔ O2(a1Δg, υ = 0) + O2(X3Σ-g, υ = 1), the information on the O2(X3Σ-g, υ = 1) kinetics is extracted from the O2(a1Δg, υ = 1) temporal evolution. In addition, measurements of the removal of O2(X3Σ-g, υ = 1) by CO2 at room temperature will also

  10. Induction of radiation resistance and radio-protective mechanism. On the reactive oxygen and free radical

    International Nuclear Information System (INIS)

    Yukawa, Osami

    2003-01-01

    Radical scavenging system for reactive oxygen species (ROS) leading to radio-protection is reviewed on findings in animals, tissues and cells. Protection against oxygen toxicity in evolution can be seen in anaerobes' superoxide dismutase (SOD) over 3500 million years ago. ROS is generated endogenously and also by radiation. However, the intracellular sites of the generated ROS are different depending on its cause. The protection is done through enzymes like SOD, peroxidase, catalase, glutathione-related enzymes and through substances like GSH, α-tocopherol, ascorbic acid etc. Induction of ROS scavenging substances related with radio-resistance includes the responses to the low dose radiation (5-50 cGy) in those enzymes described above; to middle to high dose radiation (1-30 Gy) in a similar and in other unknown mechanisms; to exposure of ROS like H 2 O 2 at low concentration; and to antioxidant treatment. The cross-resistance between radiation and drugs suggests necessity of this induction. (N.I.)

  11. Alkyl hydrogen atom abstraction reactions of the CN radical with ethanol

    Science.gov (United States)

    Athokpam, Bijyalaxmi; Ramesh, Sai G.

    2018-04-01

    We present a study of the abstraction of alkyl hydrogen atoms from the β and α positions of ethanol by the CN radical in solution using the Empirical Valence Bond (EVB) method. We have built separate 2 × 2 EVB models for the Hβ and Hα reactions, where the atom transfer is parameterized using ab initio calculations. The intra- and intermolecular potentials of the reactant and product molecules were modelled with the General AMBER Force Field, with some modifications. We have carried out the dynamics in water and chloroform, which are solvents of contrasting polarity. We have computed the potential of mean force for both abstractions in each of the solvents. They are found to have a small and early barrier along the reaction coordinate with a large energy release. Analyzing the solvent structure around the reaction system, we have found two solvents to have little effect on either reaction. Simulating the dynamics from the transition state, we also study the fate of the energies in the HCN vibrational modes. The HCN molecule is born vibrationally hot in the CH stretch in both reactions and additionally in the HCN bends for the Hα abstraction reaction. In the early stage of the dynamics, we find that the CN stretch mode gains energy at the expense of the energy in CH stretch mode.

  12. Atomic Oxygen Treatment and Its Effect on a Variety of Artist's Media

    Science.gov (United States)

    Miller, Sharon K. R.; Banks, Bruce A.; Waters, Deborah L.

    2005-01-01

    Atomic oxygen treatment has been investigated as an unconventional option for art restoration where conventional methods have not been effective. Exposure of surfaces to atomic oxygen was first performed to investigate the durability of materials in the low Earth orbit environment of space. The use of the ground based environmental simulation chambers, developed for atomic oxygen exposure testing, has been investigated in collaboration with conservators at a variety of institutions, as a method to clean the surfaces of works of art. The atomic oxygen treatment technique has been evaluated as a method to remove soot and char from the surface of oil paint (both varnished and unvarnished), watercolors, acrylic paint, and fabric as well as the removal of graffiti and other marks from surfaces which are too porous to lend themselves to conventional solvent removal techniques. This paper will discuss the treatment of these surfaces giving an example of each and a discussion of the treatment results.

  13. Characterization of a 5-eV neutral atomic oxygen beam facility

    Science.gov (United States)

    Vaughn, J. A.; Linton, R. C.; Carruth, M. R., Jr.; Whitaker, A. F.; Cuthbertson, J. W.; Langer, W. D.; Motley, R. W.

    1991-01-01

    An experimental effort to characterize an existing 5-eV neutral atomic oxygen beam facility being developed at Princeton Plasma Physics Laboratory is described. This characterization effort includes atomic oxygen flux and flux distribution measurements using a catalytic probe, energy determination using a commercially designed quadrupole mass spectrometer (QMS), and the exposure of oxygen-sensitive materials in this beam facility. Also, comparisons were drawn between the reaction efficiencies of materials exposed in plasma ashers, and the reaction efficiencies previously estimated from space flight experiments. The results of this study show that the beam facility is capable of producing a directional beam of neutral atomic oxygen atoms with the needed flux and energy to simulate low Earth orbit (LEO) conditions for real time accelerated testing. The flux distribution in this facility is uniform to +/- 6 percent of the peak flux over a beam diameter of 6 cm.

  14. New Active Optical Technique Developed for Measuring Low-Earth-Orbit Atomic Oxygen Erosion of Polymers

    Science.gov (United States)

    Banks, Bruce A.; deGroh, Kim K.; Demko, Rikako

    2003-01-01

    Polymers such as polyimide Kapton (DuPont) and Teflon FEP (DuPont, fluorinated ethylene propylene) are commonly used spacecraft materials because of desirable properties such as flexibility, low density, and in the case of FEP, a low solar absorptance and high thermal emittance. Polymers on the exterior of spacecraft in the low-Earth-orbit (LEO) environment are exposed to energetic atomic oxygen. Atomic oxygen reaction with polymers causes erosion, which is a threat to spacecraft performance and durability. It is, therefore, important to understand the atomic oxygen erosion yield E (the volume loss per incident oxygen atom) of polymers being considered in spacecraft design. The most common technique for determining E is a passive technique based on mass-loss measurements of samples exposed to LEO atomic oxygen during a space flight experiment. There are certain disadvantages to this technique. First, because it is passive, data are not obtained until after the flight is completed. Also, obtaining the preflight and postflight mass measurements is complicated by the fact that many polymers absorb water and, therefore, the mass change due to water absorption can affect the E data. This is particularly true for experiments that receive low atomic oxygen exposures or for samples that have a very low E. An active atomic oxygen erosion technique based on optical measurements has been developed that has certain advantages over the mass-loss technique. This in situ technique can simultaneously provide the erosion yield data on orbit and the atomic oxygen exposure fluence, which is needed for erosion yield determination. In the optical technique, either sunlight or artificial light can be used to measure the erosion of semitransparent or opaque polymers as a result of atomic oxygen attack. The technique is simple and adaptable to a rather wide range of polymers, providing that they have a sufficiently high optical absorption coefficient. If one covers a photodiode with a

  15. The oxygen-centered radicals scavenging activity of sulfasalazine and its metabolites. A direct protection of the bowel.

    Science.gov (United States)

    Prónai, L; Yukinobu, I; Láng, I; Fehér, J

    1992-01-01

    Oxygen-centered radicals, such as superoxide (O2-) and hydroxyl radicals (.OH) generated by phagocytes have been suggested to be involved in the pathogenesis of chronic inflammations of the bowel, such as Crohn's disease and colitis ulcerosa. Recently, sulfasalazine (SASP) and its metabolites have been reported to exert their effects as a direct scavenger of oxygen-centered radicals in the bowel. To scavenge oxygen-centered radicals in vivo, however, SASP and its metabolites have to react with O2- and/or .OH in vitro very rapidly, furthermore they have to reach an appropriate (possible millimolar) concentration range at the site of inflammation. To test this possibility, we investigated the direct O2- and .OH scavenging activity of SASP and its metabolites using the specific electron paramagnetic resonance/spin trapping method, and we compared the 50% inhibition rates of SASP and its metabolites with their known concentrations in the bowel and in the human plasma. It was found that SASP and its metabolites, such as 5-amino-salicylic acid (5-ASA), and acetyl-5-amino-salicylic acid (AC-5-ASA), but not sulfapyridine (SP) and acetyl-sulfapyridine (Ac-SP) have a direct O2- and .OH scavenging activity in vitro systems. Among the compounds, SASP and 5-ASA can reach a concentration which is appropriate to scavenge oxygen-centered radicals in the bowel but not in the human plasma. It was concluded that the in vivo antiinflammatory effects of SASP and its metabolites are, at least partly, due to the direct oxygen-centered scavenging activity of these drugs.

  16. Atomic oxygen fine-structure splittings with tunable far-infrared spectroscopy

    Science.gov (United States)

    Zink, Lyndon R.; Evenson, Kenneth M.; Matsushima, Fusakazu; Nelis, Thomas; Robinson, Ruth L.

    1991-01-01

    Fine-structure splittings of atomic oxygen (O-16) in the ground state have been accurately measured using a tunable far-infrared spectrometer. The 3P0-3pl splitting is 2,060,069.09 (10) MHz, and the 3Pl-3P2 splitting is 4,744,777.49 (16) MHz. These frequencies are important for measuring atomic oxygen concentration in earth's atmosphere and the interstellar medium.

  17. Iron halide mediated atom transfer radical polymerization of methyl methacrylate with N-Alkyl-2-pyridylmethanimine as the ligand

    NARCIS (Netherlands)

    Zhang, H.; Schubert, U.S.

    2004-01-01

    The controlled atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) catalyzed by iron halide/N-(n-hexyl)-2-pyridylmethanimine (NHPMI) is described. The ethyl 2-bromoisobutyrate (EBIB)-initiated ATRP with [MMA]0/[EBIB]0/[iron halide]0/[NHPMI]0 = 150/1/1/2 was better controlled in

  18. Ion conducting solid polymer electrolytes based on polypentafluorostyrene-b-polyether-b-polypentafluorostyrene prepared by atom transfer radical polymerization

    DEFF Research Database (Denmark)

    Jankova, Katja; Jannasch, P.; Hvilsted, Søren

    2004-01-01

    Novel triblock copolymers based on central poly( ethylene glycol) ( PEG) or poly( ethylene glycol-co-propylene glycol) (PEGPG) blocks with poly( pentafluorostyrene) (PFS) outer blocks were prepared by Atom Transfer Radical Polymerization (ATRP) with polydispersities on the order of 1.2 - 1...

  19. Synthesis of triblock and random copolymers of 4- acetoxystyrene and styrene by living atom transfer radical polymerization

    DEFF Research Database (Denmark)

    Gao, Bo; Chen, Xianyi; Ivan, Bela

    1997-01-01

    Triblock copolymers containing polystyrene (PSt) and poly(4-acetoxystyrene) (PAcOSt) segments have been prepared by atom transfer radical polymerization (ATRP). In the first step one of the two monomers was polymerized in bulk using the initiating system alpha,alpha'-dibromo-p-xylene/CuBr/2,2'-bi...

  20. Kinetics and mechanism of the gas-phase reaction of Cl atoms and OH radicals with fluorobenzene at 296 K

    DEFF Research Database (Denmark)

    Andersen, Mads Peter Sulbæk; Nielsen, Ole John; Hurley, MD

    2002-01-01

    Smog chamber/FTIR techniques were used to study the kinetics and mechanism of the reaction of Cl atoms and OH radicals with fluorobenzene, C6H5F, in 700 Torr of N-2 or air diluent at 296 K. Reaction of Cl atoms with C6H5F proceeds via two pathways: H-atom abstraction to give HCl and the C6H4F...... with Cl atoms via a mechanism which, at least in part, leads neither to production of C6H5Cl nor to reformation of C6H5F. As the steady-state Cl atom concentration is increased, the fraction of the C6H5F-Cl adduct undergoing reaction with Cl atoms increases causing an increase in the effective rate...

  1. Production of perhydroxy radical (HO2) and oxygen in the radiolysis of aqueous solution and the LET effects

    International Nuclear Information System (INIS)

    Imamura, Masashi

    1987-01-01

    This article aims to review the results concerning the production of perhydroxy radical (HO 2 ) and oxygen from irradiated aqueous solutions and the LET effects on these products, beginning with a brief introduction to the elementary primary processes in radiolysis of aqueous solution. Oxygen, if produced in the radiolysis of aqueous solution, may be considered responsible for the decreased oxygen enhancement ratio (OER) in biological systems exposed to high LET radiation. A Harwell's group has determined oxygen generated from aqueous ferrous solutions irradiated with heavy ions and concluded that the oxygen is a precursor of perhydroxy radicals. The LET-dependent yields for perhydroxy radical have been determined by LaVerne and Schuler; the analysis of their results sheds light into the reactions taking place in high-LET track cores. In conjunction with these results, the possible contributions to the LET effects are pointed out and discussed of the energetic secondary electrons ejected from the track core by knock-on collision with heavy ions and of the variation in the track core size with energy of the heavy particles. (author)

  2. A Sensitive Technique Using Atomic Force Microscopy to Measure the Low Earth Orbit Atomic Oxygen Erosion of Polymers

    Science.gov (United States)

    deGroh, Kim K.; Banks, Bruce A.; Clark, Gregory W.; Hammerstrom, Anne M.; Youngstrom, Erica E.; Kaminski, Carolyn; Fine, Elizabeth S.; Marx, Laura M.

    2001-01-01

    Polymers such as polyimide Kapton and Teflon FEP (fluorinated ethylene propylene) are commonly used spacecraft materials due to their desirable properties such as flexibility, low density, and in the case of FEP low solar absorptance and high thermal emittance. Polymers on the exterior of spacecraft in the low Earth orbit (LEO) environment are exposed to energetic atomic oxygen. Atomic oxygen erosion of polymers occurs in LEO and is a threat to spacecraft durability. It is therefore important to understand the atomic oxygen erosion yield (E, the volume loss per incident oxygen atom) of polymers being considered in spacecraft design. Because long-term space exposure data is rare and very costly, short-term exposures such as on the shuttle are often relied upon for atomic oxygen erosion determination. The most common technique for determining E is through mass loss measurements. For limited duration exposure experiments, such as shuttle experiments, the atomic oxygen fluence is often so small that mass loss measurements can not produce acceptable uncertainties. Therefore, a recession measurement technique has been developed using selective protection of polymer samples, combined with postflight atomic force microscopy (AFM) analysis, to obtain accurate erosion yields of polymers exposed to low atomic oxygen fluences. This paper discusses the procedures used for this recession depth technique along with relevant characterization issues. In particular, a polymer is salt-sprayed prior to flight, then the salt is washed off postflight and AFM is used to determine the erosion depth from the protected plateau. A small sample was salt-sprayed for AFM erosion depth analysis and flown as part of the Limited Duration Candidate Exposure (LDCE-4,-5) shuttle flight experiment on STS-51. This sample was used to study issues such as use of contact versus non-contact mode imaging for determining recession depth measurements. Error analyses were conducted and the percent probable

  3. Isolated Pt Atoms Stabilized by Amorphous Tungstenic Acid for Metal-Support Synergistic Oxygen Activation.

    Science.gov (United States)

    Zhang, Qian; Qin, Xixi; Duanmu, Fanpeng; Ji, Huiming; Shen, Zhurui; Han, Xiaopeng; Hu, Wenbin

    2018-06-05

    Oxygen activation plays a crucial role in many important chemical reactions such as organics oxidation and oxygen reduction. For developing highly active materials for oxygen activation, herein, we report an atomically dispersed Pt on WO3 nanoplates stabilized by in-situ formed amorphous H2WO4 out-layer and the mechanism for activating molecular oxygen. Experimental and theoretical studies demonstrate that the isolated Pt atoms coordinated with oxygen atoms from [WO6] and water of H2WO4, consequently leading to optimized surface electronic configuration and strong metal support interaction (SMSI). In exemplified reactions of butanone oxidation sensing and oxygen reduction, the atomic Pt/WO3 hybrid exhibits superior activity than those of Pt nanoclusters/WO3 and bare WO3 as well as enhanced long-term durability. This work will provide insight on the origin of activity and stability for atomically dispersed materials, thus promoting the development of highly efficient and durable single atom-based catalysts. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Ethylene formation from methionine as a method to evaluate oxygen free radical scavenging and metal inactivation by cosmetics.

    Science.gov (United States)

    Galey, J B; Millecamps, F; Nguyen, Q L

    1991-04-01

    Synopsis It has been proposed that oxygen free radicals are involved in skin aging. This paper describes a new method for the evaluation of oxygen free radical scavenging by cosmetic products. It is based on the measurement, by gas chromatography, of ethylene produced during the oxidation of methionine by the hydroxyl radical. OH. is produced by an iron catalyzed superoxide-driven Fenton reaction in which superoxide is obtained by photochemical oxygen reduction. The cosmetic is applied, together with methionine, riboflavine, NADH, FeCl(3) and EDTA, on a glass microfibre filter and submitted to UVA exposure through a quartz cell. Ethylene is then measured from aliquots of the atmosphere inside the cell. Catalase or Desferal completely inhibits ethylene production. SOD or high concentrations of hydroxyl radical scavengers (Mannitol, DMSO etc.) afford a partial protection. Thus the efficiency of O(2) (-)., H(2)O(2) and OH. scavengers and iron chelators can be measured. The main advantage of this test is that it is performed in conditions which simulate skin during UV exposure (e.g. air and UV exposed thin layer). Furthermore, as it is non-invasive, it can also be applied to human skin in vivo.

  5. Reaction mechanism of oxygen atoms with unsaturated hydrocarbons by the crossed molecular beams method

    Energy Technology Data Exchange (ETDEWEB)

    Buss, R.J.; Baseman, R.J.; Guozhong, H.; Lee, Y.T.

    1982-04-01

    From a series of studies of the reaction of oxygen atoms with unsaturated hydrocarbons using the crossed molecular beam method, the dominant reaction mechanisms were found to be the simple substitution reactions with oxygen atoms replacing H, Cl, Br atom or alkyl groups. Complication due to secondary reaction was avoided by carrying out experiments under single collisions and observing primary products directly. Primary products were identified by measuring the angular and velocity distributions of products at all the mass numbers which could be detected by the mass spectrometer, and from comparison of these distributions, applying the requirement of energy and momentum conservation.

  6. Reaction Mechanism of Oxygen Atoms with Unsaturated Hydrocarbons by the Crossed-Molecular-Beams Method

    Science.gov (United States)

    Buss, R. J.; Baseman, R. J.; Guozhong, H.; Lee, Y. T.

    1982-04-01

    From a series of studies of the reaction of oxygen atoms with unsaturated hydrocarbons using the crossed molecular beam method, the dominant reaction mechanisms were found to be the simple substitution reactions with oxygen atoms replacing H, Cl, Br atom or alkyl groups. Complication due to secondary reaction was avoided by carrying out experiments under single collisions and observing primary products directly. Primary products were identified by measuring the angular and velocity distributions of products at all the mass numbers which could be detected by the mass spectrometer, and from comparison of these distributions, applying the requirement of energy and momentum conservation.

  7. Passivation of CdZnTe surfaces by oxidation in low energy atomic oxygen

    International Nuclear Information System (INIS)

    Chen, H.; Chattopadhyay, K.; Chen, K.; Burger, A.; George, M.A.; Gregory, J.C.; Nag, P.K.; Weimer, J.J.; James, R.B.

    1999-01-01

    A method of surface passivation of Cd 1-x Zn x Te (CZT) x-ray and gamma ray detectors has been established by using microwave-assisted atomic oxygen bombardment. Detector performance is significantly enhanced due to the reduction of surface leakage current. CZT samples were exposed to an atomic oxygen environment at the University of Alabama in Huntsville close-quote s Thermal Atomic Oxygen Facility. This system generates neutral atomic oxygen species with kinetic energies of 0.1 - 0.2 eV. The surface chemical composition and its morphology modification due to atomic oxygen exposure were studied by x-ray photoelectron spectroscopy and atomic force microscopy and the results were correlated with current-voltage measurements and with room temperature spectral responses to 133 Ba and 241 Am radiation. A reduction of leakage current by about a factor of 2 is reported, together with significant improvement in the gamma-ray line resolution. copyright 1999 American Vacuum Society

  8. Novel atmospheric pressure plasma device releasing atomic hydrogen: reduction of microbial-contaminants and OH radicals in the air

    International Nuclear Information System (INIS)

    Nojima, Hideo; Park, Rae-Eun; Kwon, Jun-Hyoun; Suh, Inseon; Jeon, Junsang; Ha, Eunju; On, Hyeon-Ki; Kim, Hye-Ryung; Choi, KyoungHui; Lee, Kwang-Hee; Seong, Baik-Lin; Jung, Hoon; Kang, Shin Jung; Namba, Shinichi; Takiyama, Ken

    2007-01-01

    A novel atmospheric pressure plasma device releasing atomic hydrogen has been developed. This device has specific properties such as (1) deactivation of airborne microbial-contaminants, (2) neutralization of indoor OH radicals and (3) being harmless to the human body. It consists of a ceramic plate as a positive ion generation electrode and a needle-shaped electrode as an electron emission electrode. Release of atomic hydrogen from the device has been investigated by the spectroscopic method. Optical emission of atomic hydrogen probably due to recombination of positive ions, H + (H 2 O)n, generated from the ceramic plate electrode and electrons emitted from the needle-shaped electrode have been clearly observed in the He gas (including water vapour) environment. The efficacy of the device to reduce airborne concentrations of influenza virus, bacteria, mould fungi and allergens has been evaluated. 99.6% of airborne influenza virus has been deactivated with the operation of the device compared with the control test in a 1 m 3 chamber after 60 min. The neutralization of the OH radical has been investigated by spectroscopic and biological methods. A remarkable reduction of the OH radical in the air by operation of the device has been observed by laser-induced fluorescence spectroscopy. The cell protection effects of the device against OH radicals in the air have been observed. Furthermore, the side effects have been checked by animal experiments. The harmlessness of the device has been confirmed

  9. Oxygen-induced restructuring with release of gold atoms from Au(111)

    International Nuclear Information System (INIS)

    Min, B.K.; Deng, X.; Schalek, R.; Pinnaduwage, D.; Friend, C.M.

    2005-01-01

    Adsorption of oxygen atoms, achieved via electron-induced dissociation of nitrogen dioxide, induces restructuring of the 'herringbone' to a striped, soliton-wall structure accompanied by release of gold from the 'elbows' in the herringbone structure. The number density of 'elbows' (dislocations corresponding to a change in direction of the reconstruction) decreases as a function of increasing atomic oxygen coverage while the long range order observed in low energy electron diffraction (LEED) changes from (√(3)x22)-rec. to (1x22) in the limit of saturation coverage. Small islands and serrated step edges were formed due to the release of gold atoms from elbow sites of Au(111). The overall structural change of the Au(111) surface may result from the reduction of anisotropy related to the tensile stress relief of the Au(111) surface by oxygen atoms

  10. Fluorescence measurement of atomic oxygen concentration in a dielectric barrier discharge

    Science.gov (United States)

    Dvořák, P.; Mrkvičková, M.; Obrusník, A.; Kratzer, J.; Dědina, J.; Procházka, V.

    2017-06-01

    Concentration of atomic oxygen was measured in a volume dielectric barrier discharge (DBD) ignited in mixtures of Ar + O2(+ H2) at atmospheric pressure. Two-photon absorption laser induced fluorescence (TALIF) of atomic oxygen was used and this method was calibrated by TALIF of Xe in a mixture of argon and a trace of xenon. The calibration was performed at atmospheric pressure and it was shown that quenching by three-body collisions has negligible effect on the life time of excited Xe atoms. The concentration of atomic oxygen in the DBD was around 1021 m-3 and it was stable during the whole discharge period. The concentration did not depend much on the electric power delivered to the discharge provided that the power was sufficiently high so that the visible discharge filled the whole reactor volume. Both the addition of hydrogen or replacing of argon by helium led to a significant decrease of atomic oxygen concentration. The TALIF measurements of O concentration levels in the DBD plasma performed in this work are made use of e.g. in the field analytical chemistry. The results contribute to understanding the processes of analyte hydride preconcentration and subsequent atomization in the field of trace element analysis where DBD plasma atomizers are employed.

  11. Constructing Functional Ionic Membrane Surface by Electrochemically Mediated Atom Transfer Radical Polymerization

    Directory of Open Access Journals (Sweden)

    Fen Ran

    2016-01-01

    Full Text Available The sodium polyacrylate (PAANa contained polyethersulfone membrane that was fabricated by preparation of PES-NH2 via nonsolvent phase separation method, the introduction of bromine groups as active sites by grafting α-Bromoisobutyryl bromide, and surface-initiated electrochemically atom transfer radical polymerization (SI-eATRP of sodium acrylate (AANa on the surface of PES membrane. The polymerization could be controlled by reaction condition, such as monomer concentration, electric potential, polymerization time, and modifier concentration. The membrane surface was uniform when the monomer concentration was 0.9 mol/L, the electric potential was −0.12 V, the polymerization time was 8 h, and the modifier concentration was 2 wt.%. The membrane showed excellent hydrophilicity and blood compatibility. The water contact angle decreased from 84° to 68° and activated partial thromboplastin increased from 51 s to 84 s after modification of the membranes.

  12. Surface modification of nanodiamond through metal free atom transfer radical polymerization

    Energy Technology Data Exchange (ETDEWEB)

    Zeng, Guangjian; Liu, Meiying; Shi, Kexin; Heng, Chunning; Mao, Liucheng; Wan, Qing; Huang, Hongye [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); Deng, Fengjie, E-mail: fengjiedeng@aliyun.com [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); Zhang, Xiaoyong, E-mail: xiaoyongzhang1980@gmail.com [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); Wei, Yen, E-mail: weiyen@tsinghua.edu.cn [Department of Chemistry and the Tsinghua Center for Frontier Polymer Research, Tsinghua University, Beijing, 100084 (China)

    2016-12-30

    Highlights: • Surface modification of ND with water soluble and biocompatible polymers. • Functionalized ND through metal free surface initiated ATRP. • The metal free surface initiated ATRP is rather simple and effective. • The ND-poly(MPC) showed high dispersibility and desirable biocompatibility. - Abstract: Surface modification of nanodiamond (ND) with poly(2-methacryloyloxyethyl phosphorylcholine) [poly(MPC)] has been achieved by using metal free surface initiated atom transfer radical polymerization (SI-ATRP). The ATRP initiator was first immobilized on the surface of ND through direct esterification reaction between hydroxyl group of ND and 2-bromoisobutyryl bromide. The initiator could be employed to obtain ND-poly(MPC) nanocomposites through SI-ATRP using an organic catalyst. The final functional materials were characterized by {sup 1}H nuclear magnetic resonance, transmission electron microscopy, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy and thermo gravimetric analysis in detailed. All of these characterization results demonstrated that ND-poly(MPC) have been successfully obtained via metal free photo-initiated SI-ATRP. The ND-poly(MPC) nanocomposites shown enhanced dispersibility in various solvents as well as excellent biocompatibility. As compared with traditional ATRP, the metal free ATRP is rather simple and effective. More importantly, this preparation method avoided the negative influence of metal catalysts. Therefore, the method described in this work should be a promising strategy for fabrication of polymeric nanocomposites with great potential for different applications especially in biomedical fields.

  13. Surface modification of nanodiamond through metal free atom transfer radical polymerization

    International Nuclear Information System (INIS)

    Zeng, Guangjian; Liu, Meiying; Shi, Kexin; Heng, Chunning; Mao, Liucheng; Wan, Qing; Huang, Hongye; Deng, Fengjie; Zhang, Xiaoyong; Wei, Yen

    2016-01-01

    Highlights: • Surface modification of ND with water soluble and biocompatible polymers. • Functionalized ND through metal free surface initiated ATRP. • The metal free surface initiated ATRP is rather simple and effective. • The ND-poly(MPC) showed high dispersibility and desirable biocompatibility. - Abstract: Surface modification of nanodiamond (ND) with poly(2-methacryloyloxyethyl phosphorylcholine) [poly(MPC)] has been achieved by using metal free surface initiated atom transfer radical polymerization (SI-ATRP). The ATRP initiator was first immobilized on the surface of ND through direct esterification reaction between hydroxyl group of ND and 2-bromoisobutyryl bromide. The initiator could be employed to obtain ND-poly(MPC) nanocomposites through SI-ATRP using an organic catalyst. The final functional materials were characterized by 1 H nuclear magnetic resonance, transmission electron microscopy, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy and thermo gravimetric analysis in detailed. All of these characterization results demonstrated that ND-poly(MPC) have been successfully obtained via metal free photo-initiated SI-ATRP. The ND-poly(MPC) nanocomposites shown enhanced dispersibility in various solvents as well as excellent biocompatibility. As compared with traditional ATRP, the metal free ATRP is rather simple and effective. More importantly, this preparation method avoided the negative influence of metal catalysts. Therefore, the method described in this work should be a promising strategy for fabrication of polymeric nanocomposites with great potential for different applications especially in biomedical fields.

  14. Efficient Functionalization of Polyethylene Fibers for the Uranium Extraction from Seawater through Atom Transfer Radical Polymerization

    Energy Technology Data Exchange (ETDEWEB)

    Neti, Venkata S. [Chemical; Das, Sadananda [Chemical; Brown, Suree [Department; Janke, Christopher J. [Materials; Kuo, Li-Jung [Marine; Gill, Gary A. [Marine; Dai, Sheng [Chemical; Department; Mayes, Richard T. [Chemical

    2017-09-14

    Brush-on-brush structures are proposed as one method to overcome support effects in grafted polymers. Utilizing glycidyl methacrylate (GMA) grafted on polyethylene (PE) fibers using radiation-induced graft polymerization (RIGP) provides a hydrophilic surface on the hydrophobic PE. When integrated with atom transfer radical polymerization (ATRP), the grafting of acrylonitrile (AN) and hydroxyethyl acrylate (HEA) can be controlled and manipulated more easily than with RIGP. Poly(acrylonitrile)-co-poly(hydroxyethyl acrylate) chains were grown via ATRP on PE-GMA fibers to generate an adsorbent for the extraction of uranium from seawater. The prepared adsorbents in this study demonstrated promise (159.9 g- U/kg of adsorbent) in laboratory screening tests using a high uranium concentration brine and 1.24 g-U/Kg of adsorbent in the filtered natural seawater in 21-days. The modest capacity in 21- days exceeds previous efforts to generate brush-on-brush adsorbents by ATRP while manipulating the apparent surface hydrophilicity of the trunk material (PE).

  15. Formation of hyperbranched polymers in atom transfer radical copolymerization of MMA and DVB

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    Hyperbranched poly(methyl methacrylate)s (HPMMAs) have been successfully prepared by atom transfer radical copolymerization of MMA and divinylbenzene (DVB).Kinetic study shows complete consumption of the initiator in 0.5 h,and relatively low polymerization rate when DVB content in the feed was high.By analyzing MALDI-TOF spectra of the resulting copolymers,the linear A n B (n=0,1,2,3) oligomers were formed in 0.5 h of polymerization,and then the oligomers reacted each other to form dimers,further reactions produced HPMMA.The SEC and NMR spectroscopies were used to trace the polymerization,and the results demonstrate that small amount of the branching reactions occur in the initial polymerization,and the branched polymers are significantly generated past a certain conversion depending upon the feed ratios.Raising the content of DVB in the monomer mixture can increase the pendent vinyl groups of the linear oligo-inimers,leading to gelation at low MMA conversion.

  16. Poly(n-isopropylacrylamide)-based hydrogel coatings on magnetite nanoparticles via atom transfer radical polymerization

    Energy Technology Data Exchange (ETDEWEB)

    Frimpong, Reynolds A; Hilt, J Zach [Department of Chemical and Materials Engineering, University of Kentucky, Lexington, KY 40506 (United States)], E-mail: hilt@engr.uky.edu

    2008-04-30

    Core magnetite (Fe{sub 3}O{sub 4}) nanoparticles have been functionalized with a model intelligent hydrogel system based on the temperature responsive polymer poly(n-isopropyl acrylamide) (PNIPAAm) to obtain magnetically responsive core-shell nanocomposites. Fe{sub 3}O{sub 4} nanoparticles were obtained from a one-pot co-precipitation method which provided either oleic acid (hydrophobic) or citric acid (hydrophilic) coated nanoparticles. Subsequent ligand exchange of these coatings with various bromine alkyl halides and a bromo silane provided initiating sites for functionalization with NIPAAm using atom transfer radical polymerization (ATRP). The bromine alkyl halides that were used were 2-bromo-2-methyl propionic acid (BMPA) and 2-bromopropionyl bromide (BPB). The bromo silane that was used was 3-bromopropyl trimethoxysilane (BPTS). The intelligent polymeric shell consists of NIPAAm crosslinked with poly(ethylene glycol) 400 dimethacrylate (PEG400DMA). Fourier transform infrared (FTIR) spectroscopy, thermogravimetric analysis (TGA), and transmission electron microscopy (TEM) were used to confirm the presence of the polymeric shell. Dynamic light scattering (DLS) was used to characterize the nanocomposites for particle size changes with temperature. Their magnetic and temperature responsiveness show great promise for further biomedical applications. This platform for functionalizing magnetic nanoparticles with intelligent hydrogels promises to impact a wide range of medical and biological applications of magnetic nanoparticles.

  17. Colorful Polyelectrolytes: An Atom Transfer Radical Polymerization Route to Fluorescent Polystyrene Sulfonate.

    Science.gov (United States)

    Huberty, Wayne; Tong, Xiaowei; Balamurugan, Sreelatha; Deville, Kyle; Russo, Paul S; Zhang, Donghui

    2016-03-01

    A labeled green fluorescent polystyrene sulfonate (LNaPSS) has been synthesized using atom transfer radical polymerization of a styrene sulfonate monomer with a fluorescent co-monomer, fluorescein thiocyanate-vinyl aniline. As a result this 100 % sulfonated polymer contains no hydrophobic patches along the chain backbone besides the fluorescent marker itself. The concentration of the fluorescent monomer was kept low to maintain the characteristic properties of the anionic polyelectrolyte, LNaPSS. ATRP conditions facilitated the production of polymers spanning a range of molecular weights from 35,000 to 175,000 in gram-scale batches with polydispersity indices of 1.01-1.24. Molecular weight increased with the monomer to initiator ratio. Gel permeation chromatography results show a unimodal distribution, and the polymer structure was also confirmed by (1)H NMR and FT-IR spectroscopy. Fluorescence spectroscopy confirmed covalent bonding of fluorescein isothiocyanate to the polymer, indicating that the polymer is suitable as a probe in fluorescence microscopy. To demonstrate this ability, the polymer was used to locate structural features in salt crystals formed during drying, as in the evaporation of sea mist. A second application to probe diffusion studies is also demonstrated.

  18. Surface modification of nanodiamond through metal free atom transfer radical polymerization

    Science.gov (United States)

    Zeng, Guangjian; Liu, Meiying; Shi, Kexin; Heng, Chunning; Mao, Liucheng; Wan, Qing; Huang, Hongye; Deng, Fengjie; Zhang, Xiaoyong; Wei, Yen

    2016-12-01

    Surface modification of nanodiamond (ND) with poly(2-methacryloyloxyethyl phosphorylcholine) [poly(MPC)] has been achieved by using metal free surface initiated atom transfer radical polymerization (SI-ATRP). The ATRP initiator was first immobilized on the surface of ND through direct esterification reaction between hydroxyl group of ND and 2-bromoisobutyryl bromide. The initiator could be employed to obtain ND-poly(MPC) nanocomposites through SI-ATRP using an organic catalyst. The final functional materials were characterized by 1H nuclear magnetic resonance, transmission electron microscopy, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy and thermo gravimetric analysis in detailed. All of these characterization results demonstrated that ND-poly(MPC) have been successfully obtained via metal free photo-initiated SI-ATRP. The ND-poly(MPC) nanocomposites shown enhanced dispersibility in various solvents as well as excellent biocompatibility. As compared with traditional ATRP, the metal free ATRP is rather simple and effective. More importantly, this preparation method avoided the negative influence of metal catalysts. Therefore, the method described in this work should be a promising strategy for fabrication of polymeric nanocomposites with great potential for different applications especially in biomedical fields.

  19. Poly(n-isopropylacrylamide)-based hydrogel coatings on magnetite nanoparticles via atom transfer radical polymerization

    International Nuclear Information System (INIS)

    Frimpong, Reynolds A; Hilt, J Zach

    2008-01-01

    Core magnetite (Fe 3 O 4 ) nanoparticles have been functionalized with a model intelligent hydrogel system based on the temperature responsive polymer poly(n-isopropyl acrylamide) (PNIPAAm) to obtain magnetically responsive core-shell nanocomposites. Fe 3 O 4 nanoparticles were obtained from a one-pot co-precipitation method which provided either oleic acid (hydrophobic) or citric acid (hydrophilic) coated nanoparticles. Subsequent ligand exchange of these coatings with various bromine alkyl halides and a bromo silane provided initiating sites for functionalization with NIPAAm using atom transfer radical polymerization (ATRP). The bromine alkyl halides that were used were 2-bromo-2-methyl propionic acid (BMPA) and 2-bromopropionyl bromide (BPB). The bromo silane that was used was 3-bromopropyl trimethoxysilane (BPTS). The intelligent polymeric shell consists of NIPAAm crosslinked with poly(ethylene glycol) 400 dimethacrylate (PEG400DMA). Fourier transform infrared (FTIR) spectroscopy, thermogravimetric analysis (TGA), and transmission electron microscopy (TEM) were used to confirm the presence of the polymeric shell. Dynamic light scattering (DLS) was used to characterize the nanocomposites for particle size changes with temperature. Their magnetic and temperature responsiveness show great promise for further biomedical applications. This platform for functionalizing magnetic nanoparticles with intelligent hydrogels promises to impact a wide range of medical and biological applications of magnetic nanoparticles

  20. Radiation-induced damage in T4 bacteriophage: the effect of superoxid radicals and molecular oxygen. Progress report, December 1, 1977--November 30, 1978

    International Nuclear Information System (INIS)

    Samuni, A.; Chevion, M.; Halpern, Y.S.; Ilan, Y.A.; Czapski, G.

    1978-01-01

    The sensitivity of T4 bacteriophage towards γ irradiation has been studied in phosphate buffer suspensions. The spectrum of the water radicals was controlled by a careful choice of the appropriate saturating gas and the addition of radical scavengers. Thus, it was possible to distinguish between the effects of molecular oxygen and the superoxide radicals formed through its reactions. About 90 percent of the damage was caused by the water radicals formed in the bulk suspensions. These probably affected the phage proteins; only the remainder of the damage involved the viral DNA. The oxygen enhancement ratio observed was not connected in any way with the formation of the superoxide radicals. The results confirmed that the OH radicals are the reactive species, while e - /sub aq/ as well as the superoxide radical do not contribute to the radiodamage

  1. Protection by free oxygen radical scavenging enzymes against salicylate-induced embryonic malformations in vitro.

    Science.gov (United States)

    Karabulut, A K; Ulger, H; Pratten, M K

    2000-08-01

    Salicylates are among the oldest and most widely used drugs and are known to lead to foetal death, growth retardation and congenital abnormalities in experimental animals. In this study, the effects of acetyl salicylic acid (ASA), salicylic acid (SAL) and sodium salicylate (NaSAL) on early organogenesis and the interaction of these molecules with free radicals has been investigated. Postimplantation rat embryos were cultured in vitro from day 9.5 of gestation for 48 hr. ASA, SAL and NaSAL were added to whole rat serum at concentrations between 0.1 and 0.6 mg/ml. Also, the lowest effective concentration of ASA for all parameters (0.3 mg/ml) and the same concentration of NaSAL and SAL was added to the culture media in the presence of superoxide dismutase (SOD) (30 U/ml) or glutathione (0.5 micromol/ml). The growth and development of embryos was compared and each embryo was evaluated for the presence of any malformations. When compared to growth of control embryos, the salicylates decreased all growth and developmental parameters in a concentration-responsive manner. There was also a concentration-related increase in overall dysmorphology, including the incidence of haematoma in the yolk sac and neural system, open neural tube, abnormal tail torsion and the absence of fore limb bud. When SOD was added in the presence of ASA, growth and developmental parameters were improved and there was a significant decrease in the incidence of malformations. Addition of SOD also decreased the incidence of malformations in the presence of SAL, but did not effect the growth and developmental parameters of SAL and NaSAL. There was no significant difference between the embryos grown in the presence of these three molecules on the addition of glutathione. The effects of salicylates might involve free oxygen radicals by the non-enzymatic production of the highly teratogenic metabolites 2,3- and 2,5-dihydroxybenzoic acid. An enhanced production of these metabolites in embryonic tissues

  2. Atmospheric Pressure Method and Apparatus for Removal of Organic Matter with Atomic and Ionic Oxygen

    Science.gov (United States)

    Banks, Bruce A. (Inventor); Rutledge, Sharon K. (Inventor)

    1997-01-01

    A gas stream containing ionic and atomic oxygen in inert gas is used to remove organic matter from a substrate. The gas stream is formed by flowing a mixture of gaseous oxygen in an inert gas such as helium at atmospheric pressure past a high voltage, current limited, direct current arc which contacts the gas mixture and forms the ionic and atomic oxygen. The arc is curved at the cathode end and the ionic oxygen formed by the arc nearer to the anode end of the arc is accelerated in a direction towards the cathode by virtue of its charge. The relatively high mass to charge ratio of the ionic oxygen enables at least some of it to escape the arc before contacting the cathode and it is directed onto the substrate. This is useful for cleaning delicate substrates such as fine and historically important paintings and delicate equipment and the like.

  3. Electron and Oxygen Atom Transfer Chemistry of Co(II) in a Proton Responsive, Redox Active Ligand Environment.

    Science.gov (United States)

    Cook, Brian J; Pink, Maren; Pal, Kuntal; Caulton, Kenneth G

    2018-05-21

    The bis-pyrazolato pyridine complex LCo(PEt 3 ) 2 serves as a masked form of three-coordinate Co II and shows diverse reactivity in its reaction with several potential outer sphere oxidants and oxygen atom transfer reagents. N-Methylmorpholine N-oxide (NMO) oxidizes coordinated PEt 3 from LCo(PEt 3 ) 2 , but the final cobalt product is still divalent cobalt, in LCo(NMO) 2 . The thermodynamics of a variety of oxygen atom transfer reagents, including NMO, are calculated by density functional theory, to rank their oxidizing power. Oxidation of LCo(PEt 3 ) 2 with AgOTf in the presence of LiCl as a trapping nucleophile forms the unusual aggregate [LCo(PEt 3 ) 2 Cl(LiOTf) 2 ] 2 held together by Li + binding to very nucleophilic chloride on Co(III) and triflate binding to those Li + . In contrast, Cp 2 Fe + effects oxidation to trivalent cobalt, to form (HL)Co(PEt 3 ) 2 Cl + ; proton and the chloride originate from solvent in a rare example of CH 2 Cl 2 dehydrochlorination. An unexpected noncomplementary redox reaction is reported involving attack by 2e reductant PEt 3 nucleophile on carbon of the 1e oxidant radical Cp 2 Fe + , forming a P-C bond and H + ; this reaction competes in the reaction of LCo(PEt 3 ) 2 with Cp 2 Fe + .

  4. Photoprotective effect of vitamins A and E on polyamine and oxygenated free radical metabolism in hairless mouse epidermis.

    Science.gov (United States)

    Khettab, N; Amory, M C; Briand, G; Bousquet, B; Combre, A; Forlot, P; Barey, M

    1988-12-01

    The purpose of this study was to confirm the photoprotective effect on skin of vitamins A and E, due to inhibition of polyamine synthesis and production of free radicals. These variables were measured in the lumbar epidermis of the female hairless mouse subjected to UVA + B irradiation. Polyamines were assayed in epidermal homogenate by HPLC, and production of oxygenated free radicals was determined by spectrofluorometric assay of malonyl dialdehyde. It was determined that butyl-hydroxy-toluene and vitamin E inhibited production of free radicals (56% and 60%, respectively) and caused a significant reduction in polyamine biosynthesis (P less than 0.01), whereas the inhibitory effect of malonyl dialdehyde induced by vitamin A (30%) had no associated effect on polyamine metabolism.

  5. Antioxidant activity of the giant jellyfish Nemopilema nomurai measured by the oxygen radical absorbance capacity and hydroxyl radical averting capacity methods.

    Science.gov (United States)

    Harada, Kazuki; Maeda, Toshimichi; Hasegawa, Yoshiro; Tokunaga, Takushi; Ogawa, Shinya; Fukuda, Kyoko; Nagatsuka, Norie; Nagao, Keiko; Ueno, Shunshiro

    2011-01-01

    The giant jellyfish Nemopilema nomurai (reaching sizes of up to 2 m diameter and 150 kg), which forms dense blooms, has caused extensive damage to fisheries by overloading trawl nets, while its toxic nematocysts cause dermatological symptoms. Giant jellyfish are currently discarded on the grounds of pest control. However, the giant jellyfish is considered to be edible and is part of Chinese cuisine. Therefore, we investigated whether any benefits for human health may be derived from consumption of the jellyfish in order to formulate medicated diets. Antioxidant activity of Nemopilema nomurai was measured using the oxygen radical absorbance capacity (ORAC) and hydroxyl radical averting capacity (HORAC) methods. Based on the results, the ORAC value of the giant jellyfish freeze-dried sample was 541 µmol trolox equivalent (TE)/100 g and the HORAC value was 3,687 µmol gallic acid equivalent (GAE)/100 g. On the other hand, the IC50 value of hydroxyl radical scavenging activity measured by using the electron spin resonance method was 3.3%. In conclusion, the results suggest that the freeze-dried powder of the giant jellyfish Nemopilema nomurai is a potentially beneficial food for humans.

  6. Crossed-molecular-beams reactive scattering of oxygen atoms

    International Nuclear Information System (INIS)

    Baseman, R.J.

    1982-11-01

    The reactions of O( 3 P) with six prototypical unsaturated hydrocarbons, and the reaction of O( 1 D) with HD, have been studied in high-resolution crossed-molecular-beams scattering experiments with mass-spectrometric detection. The observed laboratory-product angular and velocity distributions unambiguously identify parent-daughter ion pairs, distinguish different neutral sources of the same ion, and have been used to identify the primary products of the reactions. The derived center-of-mass product angular and translational energy distributions have been used to elucidate the detailed reaction dynamics. These results demonstrate that O( 3 P)-unsaturated hydrocarbon chemistry is dominated by single bond cleavages, leading to radical products exclusively

  7. Crossed-molecular-beams reactive scattering of oxygen atoms

    Energy Technology Data Exchange (ETDEWEB)

    Baseman, R.J.

    1982-11-01

    The reactions of O(/sup 3/P) with six prototypical unsaturated hydrocarbons, and the reaction of O(/sup 1/D) with HD, have been studied in high-resolution crossed-molecular-beams scattering experiments with mass-spectrometric detection. The observed laboratory-product angular and velocity distributions unambiguously identify parent-daughter ion pairs, distinguish different neutral sources of the same ion, and have been used to identify the primary products of the reactions. The derived center-of-mass product angular and translational energy distributions have been used to elucidate the detailed reaction dynamics. These results demonstrate that O(/sup 3/P)-unsaturated hydrocarbon chemistry is dominated by single bond cleavages, leading to radical products exclusively.

  8. Locations of oxygen, nitrogen and carbon atoms in vanadium determined by neutron diffraction

    International Nuclear Information System (INIS)

    Hiraga, K.; Onozuka, T.; Hirabayashi, M.

    1977-01-01

    The occupation sites of oxygen, nitrogen, and carbon atoms dissolved interstitially in vanadium have been determined by means of neutron diffraction with use of single crystals of VOsub(0.032), VNsub(0.013) and VCsub(0.006). It is revealed that the interstitial atoms occupy, randomly, the octahedral sites in the b.c.c. host lattice of the three crystals. Neutron diffraction is advantageous for the present purpose, since the coherent scattering amplitudes of the solute atoms are much larger than that of the vanadium atom. (Auth.)

  9. Quantitative measurements of ground state atomic oxygen in atmospheric pressure surface micro-discharge array

    Science.gov (United States)

    Li, D.; Kong, M. G.; Britun, N.; Snyders, R.; Leys, C.; Nikiforov, A.

    2017-06-01

    The generation of atomic oxygen in an array of surface micro-discharge, working in atmospheric pressure He/O2 or Ar/O2 mixtures, is investigated. The absolute atomic oxygen density and its temporal and spatial dynamics are studied by means of two-photon absorption laser-induced fluorescence. A high density of atomic oxygen is detected in the He/O2 mixture with up to 10% O2 content in the feed gas, whereas the atomic oxygen concentration in the Ar/O2 mixture stays below the detection limit of 1013 cm-3. The measured O density near the electrode under the optimal conditions in He/1.75% O2 gas is 4.26  ×  1015 cm-3. The existence of the ground state O (2p 4 3 P) species has been proven in the discharge at a distance up to 12 mm away from the electrodes. Dissociative reactions of the singlet O2 with O3 and deep vacuum ultraviolet radiation, including the radiation of excimer \\text{He}2\\ast , are proposed to be responsible for O (2p 4 3 P) production in the far afterglow. A capability of the surface micro-discharge array delivering atomic oxygen to long distances over a large area is considered very interesting for various biomedical applications.

  10. Behaviour of atomic oxygen in a pulsed dielectric barrier discharge measured by laser-induced fluorescence

    Energy Technology Data Exchange (ETDEWEB)

    Ono, Ryo [High Temperature Plasma Center, University of Tokyo, 5-1-5 Kashiwanoha, Kashiwa, Chiba, 227-8568 (Japan); Yamashita, Youta [Department of Electrical Engineering, University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo, 113-8656 (Japan); Takezawa, Kei [Department of Electrical Engineering, University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo, 113-8656 (Japan); Oda, Tetsuji [Department of Electrical Engineering, University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo, 113-8656 (Japan)

    2005-08-21

    Atomic oxygen is measured in a pulsed dielectric barrier discharge (DBD) using two-photon absorption laser-induced fluorescence (TALIF). The ground-level atomic oxygen is excited to the 3p {sup 3}P state by two-photon absorption at 226 nm. Negative (-40 kV) or positive (+30 kV) pulsed DBD occurs in an O{sub 2}-N{sub 2} mixture at atmospheric pressure. The pulse width of the DBD current is approximately 50 ns. The TALIF experiment shows that the decay rate of atomic oxygen increases linearly with O{sub 2} concentration. This result proves that atomic oxygen decays mainly by the third-body reaction, O + O{sub 2} + M {yields} O{sub 3} + M. The rate coefficient of the third-body reaction is estimated to be 2.2 x 10{sup -34} cm{sup 6} s{sup -1} in the negative DBD and 0.89 x 10{sup -34} cm{sup 6} s{sup -1} in the positive DBD. It is shown that the decay rate of atomic oxygen increases linearly with humidity. This can explain the well-known fact that ozone production in DBD is suppressed by increasing humidity.

  11. Behaviour of atomic oxygen in a pulsed dielectric barrier discharge measured by laser-induced fluorescence

    International Nuclear Information System (INIS)

    Ono, Ryo; Yamashita, Youta; Takezawa, Kei; Oda, Tetsuji

    2005-01-01

    Atomic oxygen is measured in a pulsed dielectric barrier discharge (DBD) using two-photon absorption laser-induced fluorescence (TALIF). The ground-level atomic oxygen is excited to the 3p 3 P state by two-photon absorption at 226 nm. Negative (-40 kV) or positive (+30 kV) pulsed DBD occurs in an O 2 -N 2 mixture at atmospheric pressure. The pulse width of the DBD current is approximately 50 ns. The TALIF experiment shows that the decay rate of atomic oxygen increases linearly with O 2 concentration. This result proves that atomic oxygen decays mainly by the third-body reaction, O + O 2 + M → O 3 + M. The rate coefficient of the third-body reaction is estimated to be 2.2 x 10 -34 cm 6 s -1 in the negative DBD and 0.89 x 10 -34 cm 6 s -1 in the positive DBD. It is shown that the decay rate of atomic oxygen increases linearly with humidity. This can explain the well-known fact that ozone production in DBD is suppressed by increasing humidity

  12. Roles of oxygen radicals and elastase in citric acid-induced airway constriction of guinea-pigs

    OpenAIRE

    Lai, Y -L; Chiou, W -Y; Lu, F J; Chiang, L Y

    1999-01-01

    Antioxidants attenuate noncholinergic airway constriction. To further investigate the relationship between tachykinin-mediated airway constriction and oxygen radicals, we explored citric acid-induced bronchial constriction in 48 young Hartley strain guinea-pigs, divided into six groups: control; citric acid; hexa(sulphobutyl)fullerenes+citric acid; hexa(sulphobutyl)fullerenes+phosphoramidon+citric acid; dimethylthiourea (DMTU)+citric acid; and DMTU+phosphoramidon+citric acid. Hexa(sulphobutyl...

  13. Hypoxia/reoxygenation increases the permeability of endothelial cell monolayers: Role of oxygen radicals

    International Nuclear Information System (INIS)

    Inauen, W.; Payne, D.K.; Kvietys, P.R.; Granger, D.N.

    1990-01-01

    We assessed the effect of hypoxia/reoxygenation on 14C-albumin flux across endothelial monolayers. Cultured bovine pulmonary artery endothelial cells were grown to confluence on nitrocellulose filters (pore size 12 microns). The endothelialized filters were mounted in Ussing-type chambers which were filled with cell culture medium (M 199). Equimolar amounts (33 nM) of 14C-labeled and unlabeled albumin were added to the hot and cold chambers, respectively. The monolayers were then exposed to successive periods (90 min) of normoxia (pO2 145 mmHg), hypoxia (pO2 20 mmHg), and reoxygenation (pO2 145 mmHg). A gas bubbling system was used to control media pO2 and to ensure adequate mixing. Four aliquots of culture media were taken during each period in order to calculate the 14C-albumin permeability across the endothelialized filter. In some experiments, either the xanthine oxidase inhibitor, oxypurinol (10 microM), or superoxide dismutase (600 U/mL), was added to the media immediately prior to the experiments. As compared to the normoxic control period, albumin permeability was 1.5 times higher during hypoxia (p less than 0.01) and 2.3 times higher during reoxygenation (p less than 0.01). The reoxygenation-induced increase in albumin permeability was prevented by either oxypurinol or superoxide dismutase. These data indicate that xanthine oxidase-derived oxygen radicals contribute to the hypoxia/reoxygenation-induced endothelial cell dysfunction. The altered endothelial barrier function induced by hypoxia/reoxygenation is consistent with the microvascular dysfunction observed following reperfusion of ischemic tissues

  14. Materials selection for long life in LEO: a critical evaluation of atomic oxygen testing with thermal atom systems

    International Nuclear Information System (INIS)

    Koontz, S.L.; Kuminecz, J.; Leger, L.; Nordine, P.

    1988-01-01

    The use of thermal atom test methods as a materials selection and screening technique for low-Earth orbit (LEO) spacecraft is critically evaluated. The chemistry and physics of thermal atom environments are compared with the LEO environment. The relative reactivities of a number of materials determined to be in thermal atom environments are compared to those observed in LEO and in high quality LEO simulations. Reaction efficiencies measured in a new type of thermal atom apparatus are one-hundredth to one-thousandth those observed in LEO, and many materials showing nearly identical reactivities in LEO show relative reactivities differing by as much as a factor of 8 in thermal atom systems. A simple phenomenological kinetic model for the reaction of oxygen atoms with organic materials can be used to explain the differences in reactivity in different environments. Certain specific thermal test environments can be used as reliable materials screening tools. Using thermal atom methods to predict material lifetime in LEO requires direct calibration of the method against LEO data or high quality simulation data for each material

  15. Effect of early rehabilitation training on oxygen free radical generation and nerve injury in patients with cerebral hemorrhage

    Directory of Open Access Journals (Sweden)

    Zhao-Shu Liu

    2017-08-01

    Full Text Available Objective: To study the effect of early rehabilitation training combined with edaravone on oxygen free radical generation and nerve injury in patients with cerebral hemorrhage. Methods: A total of 56 patients with acute cerebral hemorrhage who were treated in Zigong Third People’s Hospital between July 2014 and March 2017 were selected and randomly divided into early rehabilitation group and routine rehabilitation group, the early rehabilitation group began the rehabilitation training 2 d after cerebral hemorrhage condition was stabilized, and routine rehabilitation group began the rehabilitation training 14 d after cerebral hemorrhage. Serum contents of oxygen free radicals, nerve injury markers and neurotrophic molecules were detected 28 d and 56 d after cerebral hemorrhage. Results: 28 d and 56 d after cerebral hemorrhage, serum MDA, AOPP, 8-OHdG, GFAP, NSE, Tf, Ft and S100B levels of early rehabilitation group were significantly lower than those of routine rehabilitation group while BDNF, NGF, NTF-α and IGF-I levels were significantly higher than those of routine rehabilitation group. Conclusion: Early rehabilitation training combined with edaravone for cerebral hemorrhage can inhibit the oxygen free radical generation, reduce the degree of nerve injury and improve the neurotrophic state.

  16. Study of the Dissociative Processes in O_2 Discharges. Development of an Atomic Oxygen Beam Source

    International Nuclear Information System (INIS)

    Pagnon, Daniel

    1992-01-01

    The first part of this work is devoted to the study of dissociative processes in an oxygen glow discharge at low pressure (0,1-5 Torr, 1-80 mA). The kinetics of oxygen atoms has been determined supported by the measurements of atomic concentrations by VUV absorption spectroscopy and actinometry. The reaction coefficients for dissociative excitation and direct excitation of oxygen atoms have been calculated using the cross sections of the literature and a previously calculated EEDF. It has been demonstrated that dissociative excitation is negligible in respect with direct excitation for dissociation rates smaller than 2,5 %. An upper limit of 20 % for dissociative rates is observed. This limit has been explained by the increase of the atomic recombination at the discharge wall with increasing wall temperature. Using all these results, we have designed and optimized a source of oxygen atoms which has then been adapted on a MBE device. The spatial distribution of the atomic density has been measured in molecular jet by laser induced fluorescence (LIF) and Resonant Multi-Photon Ionization (RMPI). A stimulated emission has been evidenced and the coefficient for this process evaluated. A model for the effusion of atoms has been developed from which the flow of atoms on the sample can be predicted. This source has already been used in industrial MBE devices for in-situ oxidation of copper films, superconductors, and substrates for VLSI high speed applications. The methodology of this work and the diagnostics developed can be applied to other kinds of discharges, of other molecular gases, to design sources of atoms for the treatment of large area samples. (author) [fr

  17. Optical measurements of atomic oxygen concentration, temperature and nitric oxide production rate in flames

    Science.gov (United States)

    Myhr, Franklin Henry

    An optical method for measuring nitric oxide (NO) production rates in flames was developed and characterized in a series of steady, one-dimensional, atmospheric-pressure laminar flames of 0.700 Hsb2/0.199 Nsb2/0.101 COsb2 or 0.700 CHsb4/0.300 Nsb2 (by moles) with dry air, with equivalence ratios from 0.79 to 1.27. Oxygen atom concentration, (O), was measured by two-photon laser-induced fluorescence (LIF), temperature was measured by ultraviolet Rayleigh scattering, and nitrogen concentration was calculated from supplied reactant flows; together this information was used to calculate the NO production rate through the thermal (Zel'dovich) mechanism. Measurements by two other techniques were compared with results from the above method. In the first comparison, gas sampling was used to measure axial NO concentration profiles, the slopes of which were multiplied by velocity to obtain total NO production rates. In the second comparison, LIF measurements of hydroxyl radical (OH) were used with equilibrium water concentrations and a partial equilibrium assumption to find (O). Nitric oxide production rates from all three methods agreed reasonably well. Photolytic interference was observed during (O) LIF measurements in all of the flames; this is the major difficulty in applying the optical technique. Photolysis of molecular oxygen in lean flames has been well documented before, but the degree of interference observed in the rich flames suggests that some other molecule is also dissociating; the candidates are OH, CO, COsb2 and Hsb2O. An extrapolative technique for removing the effects of photolysis from (O) LIF measurements worked well in all flames where NO production was significant. Using the optical method to measure NO production rates in turbulent flames will involve a tradeoff among spatial resolution, systematic photolysis error, and random shot noise. With the conventional laser system used in this work, a single pulse with a resolution of 700 mum measured NO

  18. Kinetic of the gas-phase reactions of OH radicals and Cl atoms with Diethyl Ethylphosphonate and Triethyl Phosphate

    KAUST Repository

    Laversin, H.

    2015-11-30

    In this paper, the relative-rate technique has been used to obtain rate coefficients for the reaction of two organophosphorus compounds: Triethyl phosphate (TEP) and Diethyl ethylphosphonate (DEEP) with OH radicals and Cl atoms at atmospheric pressure and at different temperatures. The calculated rate constants were fitted to the Arrhenius expression over the temperature range 298 – 352 K. The following expressions (in cm3molecule-1s-1) were obtained for the reactions of OH and CL with DEEP and TEP: kOH+DEEP= (7.84±0.65)x10-14exp((1866±824)/T), kOH+TEP = (6.54±0.42)x10-14exp((1897±626)/T), kCl+DEEP = (5.27± 0.80)x10−11exp(765±140/T) and kCl+TEP = (5.23± 0.80)x10−11exp(736± 110/T). These results show that the reaction of the studied compounds with Cl atoms proceeds more rapidly than that with OH radicals. The related tropospheric lifetimes suggest that once emitted into the atmosphere, TEP and DEEP can be removed within a few hours in areas close to their emission sources. TEP and DEEP are principally removed by OH radicals. However, in coastal areas where the Cl atoms’ concentration is higher, TEP and DEEP removal by reaction with Cl atoms could be a competitive process.

  19. Ground-Laboratory to In-Space Atomic Oxygen Correlation for the PEACE Polymers

    Science.gov (United States)

    Stambler, Arielle H.; Inoshita, Karen E.; Roberts, Lily M.; Barbagallo, Claire E.; de Groh, Kim K.; Banks, Bruce A.

    2009-01-01

    The Materials International Space Station Experiment 2 (MISSE 2) Polymer Erosion and Contamination Experiment (PEACE) polymers were exposed to the environment of low Earth orbit (LEO) for 3.95 years from 2001 to 2005. There were forty-one different PEACE polymers, which were flown on the exterior of the International Space Station (ISS) in order to determine their atomic oxygen erosion yields. In LEO, atomic oxygen is an environmental durability threat, particularly for long duration mission exposures. Although space flight experiments, such as the MISSE 2 PEACE experiment, are ideal for determining LEO environmental durability of spacecraft materials, ground-laboratory testing is often relied upon for durability evaluation and prediction. Unfortunately, significant differences exist between LEO atomic oxygen exposure and atomic oxygen exposure in ground-laboratory facilities. These differences include variations in species, energies, thermal exposures and radiation exposures, all of which may result in different reactions and erosion rates. In an effort to improve the accuracy of ground-based durability testing, ground-laboratory to in-space atomic oxygen correlation experiments have been conducted. In these tests, the atomic oxygen erosion yields of the PEACE polymers were determined relative to Kapton H using a radio-frequency (RF) plasma asher (operated on air). The asher erosion yields were compared to the MISSE 2 PEACE erosion yields to determine the correlation between erosion rates in the two environments. This paper provides a summary of the MISSE 2 PEACE experiment; it reviews the specific polymers tested as well as the techniques used to determine erosion yield in the asher, and it provides a correlation between the space and ground-laboratory erosion yield values. Using the PEACE polymers' asher to in-space erosion yield ratios will allow more accurate in-space materials performance predictions to be made based on plasma asher durability evaluation.

  20. Use of O2 airglow for calibrating direct atomic oxygen measurements from sounding rockets

    Directory of Open Access Journals (Sweden)

    G. Witt

    2009-12-01

    Full Text Available Accurate knowledge about the distribution of atomic oxygen is crucial for many studies of the mesosphere and lower thermosphere. Direct measurements of atomic oxygen by the resonance fluorescence technique at 130 nm have been made from many sounding rocket payloads in the past. This measurement technique yields atomic oxygen profiles with good sensitivity and altitude resolution. However, accuracy is a problem as calibration and aerodynamics make the quantitative analysis challenging. Most often, accuracies better than a factor 2 are not to be expected from direct atomic oxygen measurements. As an example, we present results from the NLTE (Non Local Thermodynamic Equilibrium sounding rocket campaign at Esrange, Sweden, in 1998, with simultaneous O2 airglow and O resonance fluorescence measurements. O number densities are found to be consistent with the nightglow analysis, but only within the uncertainty limits of the resonance fluorescence technique. Based on these results, we here describe how better atomic oxygen number densities can be obtained by calibrating direct techniques with complementary airglow photometer measurements and detailed aerodynamic analysis. Night-time direct O measurements can be complemented by photometric detection of the O2 (b1∑g+−X3∑g- Atmospheric Band at 762 nm, while during daytime the O2 (a1Δg−X3∑g- Infrared Atmospheric Band at 1.27 μm can be used. The combination of a photometer and a rather simple resonance fluorescence probe can provide atomic oxygen profiles with both good accuracy and good height resolution.

  1. Os radicais livres de oxigênio e as doenças pulmonares Oxygen free radicals and pulmonary disease

    Directory of Open Access Journals (Sweden)

    Dahir Ramos de Andrade Júnior

    2005-02-01

    Full Text Available Os radicais livres de oxigênio são moléculas que apresentam elétrons não pareados em sua órbita externa, capazes de transformar outras moléculas com as quais se encontram, como proteínas, carbohidratos, lípides e o ácido desoxirribonucleico. Essas moléculas são geradas em situações clínicas onde microambientes de hipóxia são seguidos por microambientes de reoxigenação. Nesse grupo estão o choque hemodinâmico, a septicemia, a resposta inflamatória sistêmica, as hepatites fulminantes, o transplante de órgãos, e a insuficiência respiratória, entre outras condições. Neste trabalho discutimos os principais conceitos sobre os radicais livres de oxigênio: os principais tipos, sua formação e a forma como atuam sobre todas as estruturas celulares provocando lesão tecidual significativa. Os principais sistemas de defesa antioxidante existentes para combater o estresse oxidativo são comentados, com destaque para a glutationa, superóxido dismutase, catalase, glutationa peroxidase e N-acetilcisteína. A influência dos radicais livres de oxigênio sobre as principais doenças pulmonares também é discutida, com ênfase nos produtos do cigarro, doença pulmonar obstrutiva crônica, asma, apnéia obstrutiva do sono e síndrome do desconforto respiratório agudo.Oxygen free radicals are molecules that present unpaired electrons in their outer orbit and can transform other molecules such as proteins, carbohydrates, lipids and deoxyribonucleic acid. Oxygen free radicals are produced in various clinical conditions in which hypoxic microenvironments are generated and reoxygenation follows. Such situations include clinical shock, septicemia, systemic inflammatory response, fulminant hepatitis, organ transplant and respiratory failure. In this review, we discuss the main concepts related to oxygen free radicals: the principal types and their formation, as well as the way in which they affect cellular structures and cause

  2. Use of Atomic Oxygen for Increased Water Contact Angles of Various Polymers for Biomedical Applications

    Science.gov (United States)

    deGroh, Kim; Berger, Lauren; Roberts, Lily

    2009-01-01

    The purpose of this study was to determine the effect of atomic oxygen (AO) exposure on the hydrophilicity of nine different polymers for biomedical applications. Atomic oxygen treatment can alter the chemistry and morphology of polymer surfaces, which may increase the adhesion and spreading of cells on Petri dishes and enhance implant growth. Therefore, nine different polymers were exposed to atomic oxygen and water-contact angle, or hydrophilicity, was measured after exposure. To determine whether hydrophilicity remains static after initial atomic oxygen exposure, or changes with higher fluence exposures, the contact angles between the polymer and water droplet placed on the polymer s surface were measured versus AO fluence. The polymers were exposed to atomic oxygen in a 100-W, 13.56-MHz radio frequency (RF) plasma asher, and the treatment was found to significantly alter the hydrophilicity of non-fluorinated polymers. Pristine samples were compared with samples that had been exposed to AO at various fluence levels. Minimum and maximum fluences for the ashing trials were set based on the effective AO erosion of a Kapton witness coupon in the asher. The time intervals for ashing were determined by finding the logarithmic values of the minimum and maximum fluences. The difference of these two values was divided by the desired number of intervals (ideally 10). The initial desired fluence was then multiplied by this result (2.37), as was each subsequent desired fluence. The flux in the asher was determined to be approximately 3.0 x 10(exp 15) atoms/sq cm/sec, and each polymer was exposed to a maximum fluence of 5.16 x 10(exp 20) atoms/sq cm.

  3. Atomic hydrogen and oxygen adsorptions in single-walled zigzag silicon nanotubes

    International Nuclear Information System (INIS)

    Chen, Haoliang; Ray, Asok K.

    2013-01-01

    Ab initio calculations have been performed to study the electronic and geometric structure properties of zigzag silicon nanotubes. Full geometry and spin optimizations have been performed without any symmetry constraints with an all electron 3-21G* basis set and the B3LYP hybrid functional. The largest zigzag SiNT studied here, (12, 0), has a binding energy per atom of 3.584 eV. Atomic hydrogen and oxygen adsorptions on (9, 0) and (10, 0) nanotubes have also been studied by optimizing the distances of the adatoms from both inside and outside the tube. The adatom is initially placed in four adsorption sites-parallel bridge (PB), zigzag bridge (ZB), hollow, and on-top site. The on-top site is the most preferred site for hydrogen atom adsorbed on (9, 0), with an adsorption energy of 3.0 eV and an optimized distance of 1.49 Å from the adatom to the nearest silicon atom. For oxygen adsorption on (9, 0), the most preferred site is the ZB site, with an adsorption energy of 5.987 eV and an optimized distance of 1.72 Å. For atomic hydrogen adsorption on (10, 0), the most preferred site is also the on-top site with an adsorption energy of 3.174 eV and an optimized distance of 1.49 Å. For adsorption of atomic oxygen on (10, 0), the most preferred site is PB site, with an adsorption energy of 6.306 eV and an optimized distance of 1.71 Å. The HOMO–LUMO gaps of (9, 0) after adsorptions of hydrogen and oxygen atoms decrease while the HOMO–LUMO gaps of (10, 0) increase after adsorption of hydrogen and oxygen

  4. Laser diagnostics of atomic hydrogen and oxygen production in rf and microwave plasma discharges

    International Nuclear Information System (INIS)

    Preppernau, B.L.

    1993-01-01

    The research for this thesis involved the application of two-photon allowed laser-induced fluorescence (TALIF) to the study of atomic hydrogen and oxygen production in industrial scale radio-frequency and microwave plasma discharge apparatus. Absolute atomic hydrogen concentration profiles were measured in a Gaseous Electronics Conference Reference Cell installed at Wright-Patterson AFB, Ohio operating with a simple H 2 discharge. Two-dimensional atomic hydrogen concentration profiles were also measured in an ASTEX HPMM microwave plasma diamond deposition reactor during actual diamond growth. In addition absolute atomic oxygen concentrations were measured in the ASTEX system. Particular attention as paid to refining the concentration calibration technique and in determining a correction to account for the collisional quenching of excited state fluorescence in high pressure gases

  5. Silicon solar cell performance deposited by diamond like carbon thin film ;Atomic oxygen effects;

    Science.gov (United States)

    Aghaei, Abbas Ail; Eshaghi, Akbar; Karami, Esmaeil

    2017-09-01

    In this research, a diamond-like carbon thin film was deposited on p-type polycrystalline silicon solar cell via plasma-enhanced chemical vapor deposition method by using methane and hydrogen gases. The effect of atomic oxygen on the functioning of silicon coated DLC thin film and silicon was investigated. Raman spectroscopy, field emission scanning electron microscopy, atomic force microscopy and attenuated total reflection-Fourier transform infrared spectroscopy were used to characterize the structure and morphology of the DLC thin film. Photocurrent-voltage characteristics of the silicon solar cell were carried out using a solar simulator. The results showed that atomic oxygen exposure induced the including oxidation, structural changes, cross-linking reactions and bond breaking of the DLC film; thus reducing the optical properties. The photocurrent-voltage characteristics showed that although the properties of the fabricated thin film were decreased after being exposed to destructive rays, when compared with solar cell without any coating, it could protect it in atomic oxygen condition enhancing solar cell efficiency up to 12%. Thus, it can be said that diamond-like carbon thin layer protect the solar cell against atomic oxygen exposure.

  6. Atmospheric reactions of methylcyclohexanes with Cl atoms and OH radicals: determination of rate coefficients and degradation products.

    Science.gov (United States)

    Ballesteros, Bernabé; Ceacero-Vega, Antonio A; Jiménez, Elena; Albaladejo, José

    2015-04-01

    As the result of biogenic and anthropogenic activities, large quantities of chemical compounds are emitted into the troposphere. Alkanes, in general, and cycloalkanes are an important chemical class of hydrocarbons found in diesel, jet and gasoline, vehicle exhaust emissions, and ambient air in urban areas. In general, the primary atmospheric fate of organic compounds in the gas phase is the reaction with hydroxyl radicals (OH). The oxidation by Cl atoms has gained importance in the study of atmospheric reactions because they may exert some influence in the boundary layer, particularly in marine and coastal environments, and in the Arctic troposphere. The aim of this paper is to study of the atmospheric reactivity of methylcylohexanes with Cl atoms and OH radicals under atmospheric conditions (in air at room temperature and pressure). Relative kinetic techniques have been used to determine the rate coefficients for the reaction of Cl atoms and OH radicals with methylcyclohexane, cis-1,4-dimethylcyclohexane, trans-1,4-dimethylcyclohexane, and 1,3,5-trimethylcyclohexane at 298 ± 2 K and 720 ± 5 Torr of air by Fourier transform infrared) spectroscopy and gas chromatography-mass spectrometry (GC-MS) in two atmospheric simulation chambers. The products formed in the reaction under atmospheric conditions were investigated using a 200-L Teflon bag and employing the technique of solid-phase microextraction coupled to a GC-MS. The rate coefficients obtained for the reaction of Cl atoms with the studied compounds are the following ones (in units of 10(-10) cm(3) molecule(-1) s(-1)): (3.11 ± 0.16), (2.89 ± 0.16), (2.89 ± 0.26), and (2.61 ± 0.42), respectively. For the reactions with OH radicals the determined rate coefficients are (in units of 10(-11) cm(3) molecule(-1) s(-1)): (1.18 ± 0.12), (1.49 ± 0.16), (1.41 ± 0.15), and (1.77 ± 0.23), respectively. The reported error is twice the standard deviation. A detailed

  7. Hot oxygen atoms: Their generation and chemistry. [Production by sputtering; reaction with butenes

    Energy Technology Data Exchange (ETDEWEB)

    Ferrieri, R.A.; Chu, Yung Y.; Wolf, A.P.

    1987-01-01

    Oxygen atoms with energies between 1 and 10 eV have been produced through ion beam sputtering from metal oxide targets. Argon ion beams were used on Ta/sub 2/O/sub 5/ and V/sub 2/O/sub 5/. Results show that some control may be exerted over the atom's kinetic energy by changing the target. Reactions of the hot O(/sup 3/P) with cis- and trans-butenes were investigated. (DLC)

  8. Generation of atomic iodine via fluorine for chemical oxygen-iodine laser

    Czech Academy of Sciences Publication Activity Database

    Jirásek, Vít; Špalek, Otomar; Čenský, Miroslav; Picková, Irena; Kodymová, Jarmila; Jakubec, Ivo

    2007-01-01

    Roč. 334, - (2007), s. 167-174 ISSN 0301-0104 R&D Projects: GA ČR GA202/05/0359 Grant - others:USAF European Office for Research and Development(XE) FA 8655-05-M-4027 Institutional research plan: CEZ:AV0Z10100523; CEZ:AV0Z40320502 Keywords : atomic iodine * atomic fluorine * chemical oxygen-iodine laser Subject RIV: BH - Optics, Masers, Lasers Impact factor: 1.805, year: 2007

  9. Mechanism and kinetics of Fe, Cr, Mo and Mn atom interaction with molecular oxygen

    International Nuclear Information System (INIS)

    Akhmadov, U.S.; Zaslonko, I.S.; Smirnov, V.N.

    1988-01-01

    Rate constants of atomic interaction of some transition metals (Fe, Cr, Mo, Mn) with molecular oxygen are measured in shock waves using the resonance atomic-absorption method. A new method for determination of the parameter γ in the modified Lambert-Beer law D=ε(lN)γ is suggested and applied. Bond strength in CrO and MoO molecules is estimated

  10. Reactivity of hydropersulfides toward the hydroxyl radical unraveled: disulfide bond cleavage, hydrogen atom transfer, and proton-coupled electron transfer.

    Science.gov (United States)

    Anglada, Josep M; Crehuet, Ramon; Adhikari, Sarju; Francisco, Joseph S; Xia, Yu

    2018-02-14

    Hydropersulfides (RSSH) are highly reactive as nucleophiles and hydrogen atom transfer reagents. These chemical properties are believed to be key for them to act as antioxidants in cells. The reaction involving the radical species and the disulfide bond (S-S) in RSSH, a known redox-active group, however, has been scarcely studied, resulting in an incomplete understanding of the chemical nature of RSSH. We have performed a high-level theoretical investigation on the reactions of the hydroxyl radical (˙OH) toward a set of RSSH (R = -H, -CH 3 , -NH 2 , -C(O)OH, -CN, and -NO 2 ). The results show that S-S cleavage and H-atom abstraction are the two competing channels. The electron inductive effect of R induces selective ˙OH substitution at one sulfur atom upon S-S cleavage, forming RSOH and ˙SH for the electron donating groups (EDGs), whereas producing HSOH and ˙SR for the electron withdrawing groups (EWGs). The H-Atom abstraction by ˙OH follows a classical hydrogen atom transfer (hat) mechanism, producing RSS˙ and H 2 O. Surprisingly, a proton-coupled electron transfer (pcet) process also occurs for R being an EDG. Although for RSSH having EWGs hat is the leading channel, S-S cleavage can be competitive or even dominant for the EDGs. The overall reactivity of RSSH toward ˙OH attack is greatly enhanced with the presence of an EDG, with CH 3 SSH being the most reactive species found in this study (overall rate constant: 4.55 × 10 12 M -1 s -1 ). Our results highlight the complexity in RSSH reaction chemistry, the extent of which is closely modulated by the inductive effect of the substituents in the case of the oxidation by hydroxyl radicals.

  11. Chemical oxygen-iodine laser with atomic iodine generated via fluorine atoms

    Czech Academy of Sciences Publication Activity Database

    Jirásek, Vít; Čenský, Miroslav; Špalek, Otomar; Kodymová, Jarmila; Picková, Irena; Jakubec, Ivo

    2008-01-01

    Roč. 345, č. 1 (2008), 14-22 ISSN 0301-0104 R&D Projects: GA ČR GA202/05/0359 Institutional research plan: CEZ:AV0Z10100523; CEZ:AV0Z40320502 Keywords : atomic iodine * atomic fluorine * chemical oxygen–iodine laser * COIL Subject RIV: BH - Optics, Masers, Lasers Impact factor: 1.961, year: 2008

  12. Light absorption and the photoformation of hydroxyl radical and singlet oxygen in fog waters

    Science.gov (United States)

    Kaur, R.; Anastasio, C.

    2017-09-01

    The atmospheric aqueous-phase is a rich medium for chemical transformations of organic compounds, in part via photooxidants generated within the drops. Here we measure light absorption, photoformation rates and steady-state concentrations of two photooxidants - hydroxyl radical (•OH) and singlet molecular oxygen (1O2*) - in 8 illuminated fog waters from Davis, California and Baton Rouge, Louisiana. Mass absorption coefficients for dissolved organic compounds (MACDOC) in the samples are large, with typical values of 10,000-15,000 cm2 g-C-1 at 300 nm, and absorption extends to wavelengths as long as 450-600 nm. While nitrite and nitrate together account for an average of only 1% of light absorption, they account for an average of 70% of •OH photoproduction. Mean •OH photoproduction rates in fogs at the two locations are very similar, with an overall mean of 1.2 (±0.7) μM h-1 under Davis winter sunlight. The mean (±1σ) lifetime of •OH is 1.6 (±0.6) μs, likely controlled by dissolved organic compounds. Including calculated gas-to-drop partitioning of •OH, the average aqueous concentration of •OH is approximately 2 × 10-15 M (midday during Davis winter), with aqueous reactions providing approximately one-third of the hydroxyl radical source. At this concentration, calculated lifetimes of aqueous organics are on the order of 10 h for compounds with •OH rate constants of 1 × 1010 M-1 s-1 or higher (e.g., substituted phenols such as syringol (6.4 h) and guaiacol (8.4 h)), and on the order of 100 h for compounds with rate constants near 1 × 109 M-1 s-1 (e.g., isoprene oxidation products such as glyoxal (152 h), glyoxylic acid (58 h), and pyruvic acid (239 h)). Steady-state concentrations of 1O2* are approximately 100 times higher than those of •OH, in the range of (0.1-3.0) × 10-13 M. Since 1O2* is a more selective oxidant than •OH, it will only react appreciably with electron-rich species such as dimethyl furan (lifetime of 2.0 h) and

  13. Energy transfers between N_2(A"3Σ) nitrogen metastable molecules and oxygen atoms and molecules

    International Nuclear Information System (INIS)

    De Souza, Antonio Rogerio

    1985-01-01

    This research thesis aims at determining reaction coefficients for energy transfers between nitrogen in its metastable status and oxygen atoms and molecules, the variation of these coefficients with respect to temperature (mainly in the 200-400 K range), products formed and more particularly branching rates of O("1S) oxygen and of NO_2. Reaction coefficients are experimentally determined by using the technique of post-discharge in flow. The experimental set-up is described and the study of the best operating conditions is reported. In the next part, the author reports the study of the energy transfer between nitrogen in its metastable status N_2(A) and oxygen molecules. Reaction coefficients are determined for the first three vibrational levels. The author then reports the study of the transfer of N_2(A) molecules on oxygen atoms in their fundamental status. Reactions coefficients and their variations are determined for the three first vibrational levels. The author describes the dissociation method and the method of detection of atomic oxygen. A kinetic model is proposed for the analysis of formed products during a post-discharge in flow, and the branching rate for the formation of O("1S) oxygen between 190 and 365 K is determined. The author finally discusses publications on the role of these reactions in the interpretation of some atmospheric phenomena

  14. Effects of exogenous oxygen derived free radicals on myocardial capillary permeability, vascular tone, and incidence of ventricular arrhythmias in the canine heart

    DEFF Research Database (Denmark)

    Svendsen, Jesper Hastrup; Bjerrum, P J

    1992-01-01

    The aim was to examine the effects of exogenous oxygen derived free radicals on myocardial capillary permeability for a small hydrophilic indicator, postischaemic vascular tone, and the occurrence of arrhythmias in the canine heart in vivo.......The aim was to examine the effects of exogenous oxygen derived free radicals on myocardial capillary permeability for a small hydrophilic indicator, postischaemic vascular tone, and the occurrence of arrhythmias in the canine heart in vivo....

  15. The surface reactivity of acrylonitrile with oxygen atoms on an analogue of interstellar dust grains

    Science.gov (United States)

    Kimber, Helen J.; Toscano, Jutta; Price, Stephen D.

    2018-06-01

    Experiments designed to reveal the low-temperature reactivity on the surfaces of interstellar dust grains are used to probe the heterogeneous reaction between oxygen atoms and acrylonitrile (C2H3CN, H2C=CH-CN). The reaction is studied at a series of fixed surface temperatures between 14 and 100 K. After dosing the reactants on to the surface, temperature-programmed desorption, coupled with time-of-flight mass spectrometry, reveals the formation of a product with the molecular formula C3H3NO. This product results from the addition of a single oxygen atom to the acrylonitrile reactant. The oxygen atom attack appears to occur exclusively at the C=C double bond, rather than involving the cyano(-CN) group. The absence of reactivity at the cyano site hints that full saturation of organic molecules on dust grains may not always occur in the interstellar medium. Modelling the experimental data provides a reaction probability of 0.007 ± 0.003 for a Langmuir-Hinshelwood style (diffusive) reaction mechanism. Desorption energies for acrylonitrile, oxygen atoms, and molecular oxygen, from the multilayer mixed ice their deposition forms, are also extracted from the kinetic model and are 22.7 ± 1.0 kJ mol-1 (2730 ± 120 K), 14.2 ± 1.0 kJ mol-1 (1710 ± 120 K), and 8.5 ± 0.8 kJ mol-1 (1020 ± 100 K), respectively. The kinetic parameters we extract from our experiments indicate that the reaction between atomic oxygen and acrylonitrile could occur on interstellar dust grains on an astrophysical time-scale.

  16. PREPARATION OF BLOCK COPOLYMERS OF POLY(STYRENE) AND POLY(T-BUTYL ACRYLATE) OF VARIOUS MOLECULAR WEIGHTS AND ARCHITECTURES BY ATOM TRANSFER RADICAL POLYMERIZATION. (R826735)

    Science.gov (United States)

    Block copolymers of polystyrene and poly(t-butyl acrylate) were prepared using atom transfer radical polymerization techniques. These polymers were synthesized with a CuBr/N,N,N,NInactivation of catalase by free radicals derived from oxygen via gamma radiolysis

    International Nuclear Information System (INIS)

    Malhaire, J.P.; Gardes-Albert, M.; Ferradini, C.; Sabourault, D.; Ribiere, C.

    1991-01-01

    The inactivation of catalase (10 -5 mol/l) by OH· or OH·/O 2 - · free radicals, at pH 7.4, has been investigated using γ radiolysis with doses up to 9000 Gy. Maxima initial G-values of catalase inactivation have been determined. These values are inferior to those of the free radicals OH· and O 2 - · produced by water radiolysis. Nevertheless, the presence of O 2 /O 2 - · enhances the inactivation due to OH· radicals. The general shape of the inactivation curves as a function of the radiation dose is biphasic: an initial rapid phase (from 0 to ∼ 500 Gy) followed by a slow phase (from ∼ 500 to 9000 Gy). The addition of H 2 O 2 at the beginning of irradiation decreases the inactivation yield by OH· radicals. This phenomenon could be due to the formation of compound-I (catalase-H 2 O 2 ) which would be less sensitive towards OH· radicals than catalase. In the presence of 0.1 mol/l ethanol, catalase (5 x 10 -6 mol/l) is not inactived by O 2 - · and RO 2 · (from ethanol) radicals for an irradiation dose of 2000 Gy, implying a complete protecting effect by ethanol [fr

  17. Adsorption of atomic oxygen (N2O) on a clean Ge(001) surface

    NARCIS (Netherlands)

    Zandvliet, Henricus J.W.; Keim, Enrico G.; van Silfhout, Arend

    1990-01-01

    We present the results of a study concerning the interaction of atomic oxygen (as released by decomposition of N2O ) with the clean Ge(001)2×1 surface at 300 K. Ellipsometry in the photon energy range of 1.5–4 eV, surface conductance measurements and Auger electron spectroscopy(AES) have been used

  18. Atomic Oxygen Treatment as a Method of Recovering Smoke Damaged Paintings

    Science.gov (United States)

    Rutledge, Sharon K.; Banks, Bruce A.; Forkapa, Mark; Stueber, Thomas; Sechkar, Edward; Malinowski, Kevin

    1998-01-01

    Smoke damage, as a result of a fire, can be difficult to remove from some types of painting media without causing swelling, leaching or pigment movement or removal. A non-contact technique has been developed which can remove soot from the surface of a painting by use of a gently flowing gas containing atomic oxygen. The atomic oxygen chemically reacts with the soot on the surface creating gasses such as carbon monoxide and carbon dioxide which can be removed through the use of an exhaust system. The reaction is limited to the surface so that the process can be timed to stop when the paint layer is reached. Atomic oxygen is a primary component of the low Earth orbital environment, but can be generated on Earth through various methods. This paper will discuss the results of atomic oxygen treatment of soot exposed acrylic gesso, ink on paper, and a varnished oil painting. Reflectance measurements were used to characterize the surfaces before and after treatment.

  19. Rate of reaction of dimethylmercury with oxygen atoms in the gas phase

    DEFF Research Database (Denmark)

    Egsgaard, Helge

    1986-01-01

    The rate constant for the reaction of atomic oxygen (O(3P)) with dimethylmercury has been measured at room temperature at a pressure of about 1 Torr using a fast flow system with electron paramagnetic resonance and mass spectrometric detection. Some reaction products were identified. The rate...

  1. Energy variable monoenergetic positron beam study of oxygen atoms in Czochralski grown Si

    International Nuclear Information System (INIS)

    Tanigawa, S.; Wei, L.; Tabuki, Y.; Nagai, R.; Takeda, E.

    1992-01-01

    A monoenergetic positron beam has been used to investigate the state of interstitial oxygen in Czochralski-grown Si with the coverage of SiO 2 (100 nm) and poly-Si (200 nm)/SiO 2 (100 nm), respectively. It was found that (i) the growth of SiO 2 gives rise to a strong Doppler broadening of positron annihilation radiations in the bulk of Si, (ii) such a broadening can be recovered to the original level by annealing at 450degC, by the removal of overlayers using chemical etching and long-term aging at room temperature, (iii) the film stress over the CZ-grown Si is responsible for the rearrangement of oxygen atoms in S and (iv) only tensile stress gives rise to the clustering of oxygen atoms. The observed broadening was assigned to arise from the positron trapping by oxygen interstitial clusters. It was concluded that film stress is responsible for the rearrangement of oxygen atoms in CZ-grown Si. (author)

  2. Atomic oxygen production scaling in a nanosecond-pulsed externally grounded dielectric barrier plasma jet

    Science.gov (United States)

    Sands, Brian; Schmidt, Jacob; Ganguly, Biswa; Scofield, James

    2014-10-01

    Atomic oxygen production is studied in a capillary dielectric barrier plasma jet that is externally grounded and driven with a 20-ns risetime positive unipolar pulsed voltage at pulse repetition rates up to 25 kHz. The power coupled to the discharge can be easily increased by increasing the pulse repetition rate. At a critical turnover frequency, determined by the net energy density coupled to the discharge, the plasma chemistry abruptly changes. This is indicated by increased plasma conductance and a transition in reactive oxygen species production from an ozone-dominated production regime below the turnover frequency to atomic-oxygen-dominated production at higher pulse rates. Here, we characterize atomic oxygen production scaling using spatially- and temporally-resolved two-photon absorption laser-induced-fluorescence (TALIF). Quantitative results are obtained via calibration with xenon using a similar laser excitation and collection system. These results are compared with quantitative ozone and discharge power measurements using a helium gas flow with oxygen admixtures up to 3%.

  3. Atomic oxygen dynamics in an air dielectric barrier discharge: a combined diagnostic and modeling approach

    Science.gov (United States)

    Baldus, Sabrina; Schröder, Daniel; Bibinov, Nikita; Schulz-von der Gathen, Volker; Awakowicz, Peter

    2015-06-01

    Cold atmospheric pressure plasmas are a promising alternative therapy for treatment of chronic wounds, as they have already shown in clinical trials. In this study an air dielectric barrier discharge (DBD) developed for therapeutic use in dermatology is characterized with respect to the plasma produced reactive oxygen species, namely atomic oxygen and ozone, which are known to be of great importance to wound healing. To understand the plasma chemistry of the applied DBD, xenon-calibrated two-photon laser-induced fluorescence spectroscopy and optical absorption spectroscopy are applied. The measured spatial distributions are shown and compared to each other. A model of the afterglow chemistry based on optical emission spectroscopy is developed to cross-check the measurement results and obtain insight into the dynamics of the considered reactive oxygen species. The atomic oxygen density is found to be located mostly between the electrodes with a maximum density of {{n}\\text{O}}=6× {{10}16} cm-3 . Time resolved measurements reveal a constant atomic oxygen density between two high voltage pulses. The ozone is measured up to 3 mm outside the active plasma volume, reaching a maximum value of {{n}{{\\text{O}3}}}=3× {{10}16} cm-3 between the electrodes.

  4. Molecular Ions in Ion Upflows and their Effects on Hot Atomic Oxygen Production

    Science.gov (United States)

    Foss, V.; Yau, A. W.; Shizgal, B.

    2017-12-01

    We present new direct ion composition observations of molecular ions in auroral ion upflows from the CASSIOPE Enhanced Polar Outflow Probe (e-POP). These observed molecular ions are N2+, NO+, and possibly O2+, and are found to occur at all e-POP altitudes starting at about 400 km, during auroral substorms and the different phases of magnetic storms, sometimes with upflow velocities exceeding a few hundred meters per second and abundances of 5-10%. The dissociative recombination of both O2+ and NO+ was previously proposed as an important source of hot oxygen atoms in the topside thermosphere [Hickey et al., 1995]. We investigate the possible effect of the observed molecular ions on the production of hot oxygen atoms in the storm and substorm-time auroral thermosphere. We present numerical solutions of the Boltzmann equation for the steady-state oxygen energy distribution function, taking into account both the production of the hot atoms and their subsequent collisional relaxation. Our result suggests the formation of a hot oxygen population with a characteristic temperature on the order of 0.3 eV and constituting 1-5% of the oxygen density near the exobase. We discuss the implication of this result in the context of magnetosphere-ionosphere-thermosphere coupling.

  5. Surface coverage of Pt atoms on PtCo nanoparticles and catalytic kinetics for oxygen reduction

    Energy Technology Data Exchange (ETDEWEB)

    Jiang Rongzhong, E-mail: rongzhong.jiang@us.army.mi [Sensors and Electron Devices Directorate, U.S. Army Research Laboratory, 2800 Powder Mill Road, Adelphi, MD 20783-1197 (United States); Rong, Charles; Chu, Deryn [Sensors and Electron Devices Directorate, U.S. Army Research Laboratory, 2800 Powder Mill Road, Adelphi, MD 20783-1197 (United States)

    2011-02-01

    The surface coverage of Pt atoms on PtCo nanoparticles and its effect on catalytic kinetics for oxygen reduction were investigated. The PtCo nanoparticles with different surface coverage of Pt atoms were synthesized with various methods, including normal chemical method, microemulsion synthesis, and ultrasound-assisted microemulsion. A model of Pt atoms filling into a spherical nanoparticle was proposed to explain the relationship of surface metal atoms and nanoparticle size. The catalytic activity of the PtCo nano-particles is highly dependent on the synthetic methods, even if they have the same chemical composition. The PtCo nano-particles synthesized with ultrasound-assisted microemulsion showed the highest activity, which is attributed to an increase of active surface coverage of Pt atoms on the metal nanoparticles. The rate of oxygen reduction at 0.5 V (vs. SCE) catalyzed by the PtCo synthesized with ultrasound-assisted micro-emulsion was about four times higher than that of the PtCo synthesized with normal chemical method. As demonstrated with rotating-ring disk electrode measurement, the PtCo nano-particles can catalyze oxygen 4-electron reduction to water without intermediate H{sub 2}O{sub 2} detected.

  6. Atomic structure of diamond {111} surfaces etched in oxygen water vapor

    International Nuclear Information System (INIS)

    Theije, F.K. de; Reedijk, M.F.; Arsic, J.; Enckevort, W.J.P. van; Vlieg, E.

    2001-01-01

    The atomic structure of the {111} diamond face after oxygen-water-vapor etching is determined using x-ray scattering. We find that a single dangling bond diamond {111} surface model, terminated by a full monolayer of -OH fits our data best. To explain the measurements it is necessary to add an ordered water layer on top of the -OH terminated surface. The vertical contraction of the surface cell and the distance between the oxygen atoms are generally in agreement with model calculations and results on similar systems. The OH termination is likely to be present during etching as well. This model experimentally confirms the atomic-scale mechanism we proposed previously for this etching system

  7. Esterified dendritic TAM radicals with very high stability and enhanced oxygen sensitivity.

    Science.gov (United States)

    Song, Yuguang; Liu, Yangping; Hemann, Craig; Villamena, Frederick A; Zweier, Jay L

    2013-02-15

    In this work, we have developed a new class of dendritic TAM radicals (TG, TdG, and dTdG) through a convergent method based on the TAM core CT-03 or its deuterated analogue dCT-03 and trifurcated Newkome-type monomer. Among these radicals, dTdG exhibits the best EPR properties with sharpest EPR singlet and highest O(2) sensitivity due to deuteration of both the ester linker groups and the TAM core CT-03. Like the previous dendritic TAM radicals, these new compounds also show extremely high stability toward various reactive species owing to the dendritic encapsulation. The highly charged nature of these molecules resulting from nine carboxylate groups prevents concentration-dependent EPR line broadening at physiological pH. Furthermore, we demonstrate that these TAM radicals can be easily derivatized (e.g., PEGylation) at the nine carboxylate groups and the resulting PEGylated analogue dTdG-PEG completely inhibits the albumin binding, thereby enhancing suitability for in vivo applications. These new dendritic TAM radicals show great potential for in vivo EPR oximetric applications and provide insights on approaches to develop improved and targeted EPR oximetric probes for biomedical applications.

  8. The scavenging of free radical and oxygen species activities and hydration capacity of collagen hydrolysates from walleye pollock ( Theragra chalcogramma) skin

    Science.gov (United States)

    Zhuang, Yongliang; Li, Bafang; Zhao, Xue

    2009-06-01

    Fish skin collagen hydrolysates (FSCH) were prepared from walleye pollock ( Theragra chalcogramma) using a mixture of enzymes, namely trypsin and flavourzyme. The degree of hydrolysis of the skin collagen was 27.3%. FSCH was mainly composed of low-molecular-weight peptides and the relative proportion of <1000Da fraction was 70.6%. Free radical and oxygen species scavenging activities of FSCH were investigated in four model systems, including diphenylpicrylhy-drazyl radical (DPPH), superoxide anion radical, hydroxyl radical and hydrogen peroxide model, and compared with that of a native antioxidant, reduced glutathione (GSH). FSCH was also evaluated by water-absorbing and water-holding capacity. The results showed that FSCH was able to scavenge free radical and oxygen species significantly and to enhance water-absorbing and water-holding capacity remarkably. Therefore, FSCH may have potential applications in the medicine and food industries.

  9. Atomic and molecular oxygen adsorbed on (111) transition metal surfaces: Cu and Ni

    Energy Technology Data Exchange (ETDEWEB)

    López-Moreno, S., E-mail: sinlopez@uacam.mx [Centro de Investigación en Corrosión, Universidad Autónoma de Campeche, Av. Héroe de Nacozari 480, Campeche, Campeche 24029 (Mexico); Romero, A. H. [Physics Department, West Virginia University, Morgantown, West Virginia 26506-6315 (United States)

    2015-04-21

    Density functional theory is used to investigate the reaction of oxygen with clean copper and nickel [111]-surfaces. We study several alternative adsorption sites for atomic and molecular oxygen on both surfaces. The minimal energy geometries and adsorption energies are in good agreement with previous theoretical studies and experimental data. From all considered adsorption sites, we found a new O{sub 2} molecular precursor with two possible dissociation paths on the Cu(111) surface. Cross barrier energies for the molecular oxygen dissociation have been calculated by using the climbing image nudge elastic band method, and direct comparison with experimental results is performed. Finally, the structural changes and adsorption energies of oxygen adsorbed on surface when there is a vacancy nearby the adsorption site are also considered.

  10. Atomic and molecular oxygen adsorbed on (111) transition metal surfaces: Cu and Ni

    Science.gov (United States)

    López-Moreno, S.; Romero, A. H.

    2015-04-01

    Density functional theory is used to investigate the reaction of oxygen with clean copper and nickel [111]-surfaces. We study several alternative adsorption sites for atomic and molecular oxygen on both surfaces. The minimal energy geometries and adsorption energies are in good agreement with previous theoretical studies and experimental data. From all considered adsorption sites, we found a new O2 molecular precursor with two possible dissociation paths on the Cu(111) surface. Cross barrier energies for the molecular oxygen dissociation have been calculated by using the climbing image nudge elastic band method, and direct comparison with experimental results is performed. Finally, the structural changes and adsorption energies of oxygen adsorbed on surface when there is a vacancy nearby the adsorption site are also considered.

  11. Atomic and molecular oxygen adsorbed on (111) transition metal surfaces: Cu and Ni

    International Nuclear Information System (INIS)

    López-Moreno, S.; Romero, A. H.

    2015-01-01

    Density functional theory is used to investigate the reaction of oxygen with clean copper and nickel [111]-surfaces. We study several alternative adsorption sites for atomic and molecular oxygen on both surfaces. The minimal energy geometries and adsorption energies are in good agreement with previous theoretical studies and experimental data. From all considered adsorption sites, we found a new O 2 molecular precursor with two possible dissociation paths on the Cu(111) surface. Cross barrier energies for the molecular oxygen dissociation have been calculated by using the climbing image nudge elastic band method, and direct comparison with experimental results is performed. Finally, the structural changes and adsorption energies of oxygen adsorbed on surface when there is a vacancy nearby the adsorption site are also considered

  12. Hydrogen gas alleviates oxygen toxicity by reducing hydroxyl radical levels in PC12 cells.

    Directory of Open Access Journals (Sweden)

    Junchao Yu

    Full Text Available Hyperbaric oxygen (HBO therapy through breathing oxygen at the pressure of above 1 atmosphere absolute (ATA is useful for varieties of clinical conditions, especially hypoxic-ischemic diseases. Because of generation of reactive oxygen species (ROS, breathing oxygen gas at high pressures can cause oxygen toxicity in the central nervous system, leading to multiple neurological dysfunction, which limits the use of HBO therapy. Studies have shown that Hydrogen gas (H2 can diminish oxidative stress and effectively reduce active ROS associated with diseases. However, the effect of H2 on ROS generated from HBO therapy remains unclear. In this study, we investigated the effect of H2 on ROS during HBO therapy using PC12 cells. PC12 cells cultured in medium were exposed to oxygen gas or mixed oxygen gas and H2 at 1 ATA or 5 ATA. Cells viability and oxidation products and ROS were determined. The data showed that H2 promoted the cell viability and inhibited the damage in the cell and mitochondria membrane, reduced the levels of lipid peroxidation and DNA oxidation, and selectively decreased the levels of •OH but not disturbing the levels of O2•-, H2O2, or NO• in PC12 cells during HBO therapy. These results indicated that H2 effectively reduced •OH, protected cells against oxygen toxicity resulting from HBO therapy, and had no effect on other ROS. Our data supported that H2 could be potentially used as an antioxidant during HBO therapy.

  13. Highly Functionalized Cyclopentane Derivatives by Tandem Michael Addition/Radical Cyclization/Oxygenation Reactions

    Czech Academy of Sciences Publication Activity Database

    Holan, Martin; Pohl, Radek; Císařová, I.; Klepetářová, Blanka; Jones, P. G.; Jahn, Ullrich

    2015-01-01

    Roč. 21, č. 27 (2015), s. 9877-9888 ISSN 0947-6539 R&D Projects: GA ČR GA13-40188S Institutional support: RVO:61388963 Keywords : cyclization * domino reactions * electron transfer * Michael addition * radical reactions Subject RIV: CC - Organic Chemistry Impact factor: 5.771, year: 2015

  14. Ethylbenzene induces microsomal oxygen free radical generation: antibody-directed characterization of the responsible cytochrome P450 enzymes.

    Science.gov (United States)

    Serron, S C; Dwivedi, N; Backes, W L

    2000-05-01

    Small aromatic hydrocarbons cause changes in oxidative metabolism by modulating the levels of cytochrome P450 enzymes, with the changes in these enzymes being responsible for qualitative changes in aromatic hydrocarbon metabolism. The goal of this study was to determine if exposure to the small alkylbenzene ethylbenzene (EB) leads to an increase in hepatic free radical production. Male F344 rats were treated with ip injections of EB (10 mmol/kg) and compared to corn oil controls. Hepatic free radical production was examined by measuring the conversion of 2',7'-dichlorofluorescin diacetate (DCFH-DA) to its fluorescent product 2',7'-dichlorofluorescein (DCF). A significant elevation of fluorescent DCF production was observed after treatment with EB, despite the lack of effect on overall cytochrome P450 levels. This process was shown to be inhibitable by metyrapone, an inhibitor of P450. DCF production was also inhibited by catalase, suggesting that hydrogen peroxide (H(2)O(2)) is one of the reactive oxygen intermediates involved in EB-mediated reactive oxygen species (ROS) formation. Interestingly, superoxide dismutase (SOD) did not inhibit DCF production in corn oil-treated rats but was an effective inhibitor in the EB-treated groups. In an effort to determine if the increase in ROS production was related to changes in specific P450 enzymes, DCF production was measured in the presence of anti-CYP2B, anti-CYP2C11, anti-CYP2E1, and anti-CYP3A2 inhibitory antibodies. Anti-CYP2B antibodies inhibited DCF production in EB-treated, but not corn oil groups, which is consistent with the low constitutive levels of this enzyme and its induction by EB. The data also demonstrate that CYP2B contributes to ROS production. Anti-CYP2C11 did not influence DCF production in either group. ROS formation in corn oil-treated rats as well as in ethylbenzene-treated rats was also inhibited with antibodies to anti-CYP2E1 and anti-CYP3A2. These results suggest that CYP2C11 does not appear to

  15. Oxidation of Ni(Pt)Si by molecular vs. atomic oxygen

    International Nuclear Information System (INIS)

    Manandhar, Sudha; Copp, Brian; Kelber, J.A.

    2008-01-01

    X-ray photoelectron spectroscopy (XPS) has been used to characterize the oxidation of a clean Ni(Pt)Si surface under two distinct conditions: exposure to a mixed flux of atomic and molecular oxygen (O + O 2 ; P O+O 2 = 5 x 10 -6 Torr) and pure molecular oxygen (O 2 ; P O 2 = 10 -5 Torr) at ambient temperatures. Formation of the clean, stoichiometric (nickel monosilicide) phase under vacuum conditions results in the formation of a surface layer enriched in PtSi. Oxidation of this surface in the presence of atomic oxygen initially results in formation of a silicon oxide overlayer. At higher exposures, kinetically limited oxidation of Pt results in Pt silicate formation. No passivation of oxygen uptake of the sample is observed for total O + O 2 exposure 4 L, at which point the average oxide/silicate overlayer thickness is 23 (3) A (uncertainty in the last digit in parentheses). In contrast, exposure of the clean Ni(Pt)Si surface to molecular oxygen only (maximum exposure: 5 x 10 5 L) results in slow growth of a silicon oxide overlayer, without silicate formation, and eventual passivation at a total average oxide thickness of 8(1) A, compared to a oxide average thickness of 17(2) A (no silicate formation) for the as-received sample (i.e., exposed to ambient.) The aggressive silicon oxidation by atomic oxygen, results in Ni-rich silicide formation in the substrate and the kinetically limited oxidation of the Pt

  16. Ab initio atomic thermodynamics investigation on oxygen defects in the anatase TiO{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Cheng, Zhijun [College of Science, University of Shanghai for Science and Technology, Shanghai 200093 (China); Liu, Tingyu, E-mail: liutyyxj@163.com [College of Science, University of Shanghai for Science and Technology, Shanghai 200093 (China); Yang, Chenxing; Gan, Haixiu [College of Science, University of Shanghai for Science and Technology, Shanghai 200093 (China); Chen, Jianyu [Key Laboratory of Materials for High Power Laser, Shanghai Institute of Optics and Fine Mechanics, Chinese Academy of Sciences, Shanghai 201800 (China); Zhang, Feiwu [Nanochemistry Research Institute, Curtin University, GPO Box U1987, Perth, WA 6845 (Australia)

    2013-01-05

    Highlights: Black-Right-Pointing-Pointer Three typical oxygen defects under the different annealing conditions have been studied. Black-Right-Pointing-Pointer The oxygen vacancy is easier to form at the surface than in the bulk. Black-Right-Pointing-Pointer The adsorption of O{sub 2} whose orientation is parallel to the surface should be more favorable. Black-Right-Pointing-Pointer The reduction reaction may firstly undertake at the surface during the annealing treatment. Black-Right-Pointing-Pointer The interstitial oxygen has important contribution to lead to the reduction of the band gap. - Abstract: In the framework of the ab initio atomic thermodynamics, the preliminary analysis of the oxygen defects in anatase TiO{sub 2} has been done by investigating the influence of the annealing treatment under representative conditions on three typical oxygen defects, that is, oxygen vacancy, oxygen adsorption and oxygen interstitial. Our results in this study agree well with the related experimental results. The molecular species of the adsorbed O{sub 2} is subject to the ratio of the number of the O{sub 2} to that of the vacancy, as well as to the initial orientation of O{sub 2} relative to the surface (101). Whatever the annealing condition is, the oxygen vacancy is easier to form at the surface than in the bulk indicating that the reduction reaction may firstly undertake at the surface during the annealing treatment, which is consistent with the phase transformation experiments. The molecular ion, peroxide species, caused by the interstitial oxygen has important contribution to the top of the valence band and lead to the reduction of the band gap.

  17. Insertion of molecular oxygen into a palladium(II) methyl bond: a radical chain mechanism involving palladium(III) intermediates.

    Science.gov (United States)

    Boisvert, Luc; Denney, Melanie C; Hanson, Susan Kloek; Goldberg, Karen I

    2009-11-04

    The reaction of (bipy)PdMe(2) (1) (bipy = 2,2'-bipyridine) with molecular oxygen results in the formation of the palladium(II) methylperoxide complex (bipy)PdMe(OOMe) (2). The identity of the product 2 has been confirmed by independent synthesis. Results of kinetic studies of this unprecedented oxygen insertion reaction into a palladium alkyl bond support the involvement of a radical chain mechanism. Reproducible rates, attained in the presence of the radical initiator 2,2'-azobis(2-methylpropionitrile) (AIBN), reveal that the reaction is overall first-order (one-half-order in both [1] and [AIBN], and zero-order in [O(2)]). The unusual rate law (half-order in [1]) implies that the reaction proceeds by a mechanism that differs significantly from those for organic autoxidations and for the recently reported examples of insertion of O(2) into Pd(II) hydride bonds. The mechanism for the autoxidation of 1 is more closely related to that found for the autoxidation of main group and early transition metal alkyl complexes. Notably, the chain propagation is proposed to proceed via a stepwise associative homolytic substitution at the Pd center of 1 with formation of a pentacoordinate Pd(III) intermediate.

  18. Oxidation of MoS2 by thermal and hyperthermal atomic oxygen

    International Nuclear Information System (INIS)

    Cross, J.B.; Martin, J.A.; Pope, L.E.; Koontz, S.L.

    1989-01-01

    The present study shows that, at 1.5 eV O-atom translational energy, SO 2 is generated and outgases from an anhydrous MoS 2 surface with a reactivity nearly that of kapton. The reaction of atomic oxygen with MoS 2 has little or no translational energy barrier; i.e., thermally generated atomic oxygen reacts as readily as that having 1.5 eV of translational energy. It is also shown that water present in the flowing afterglow apparatus used to study thermal O-atom reactivity formed sulfates on the MoS 2 surface and that the sulfate is most likely in the form of sulfuric acid. These results imply that water dumps or outgasing in low earth orbit have the potential of forming sulfuric acid covered surfaces on MoS 2 lubricants. Friction measurements show a high initial friction coefficient (0.2) for O-atom exposed MoS 2 surfaces which drops to the normal low value (0.05) after several cycles of operation

  19. The Kinetics of Oxygen Atom Recombination in the Presence of Carbon Dioxide

    Science.gov (United States)

    Jamieson, C. S.; Garcia, R. M.; Pejakovic, D.; Kalogerakis, K.

    2009-12-01

    Understanding processes involving atomic oxygen is crucial for the study and modeling of composition, energy transfer, airglow, and transport dynamics in planetary atmospheres. Significant gaps and uncertainties exist in the understanding of these processes and often the relevant input from laboratory measurements is missing or outdated. We are conducting laboratory experiments to measure the rate coefficient for O + O + CO2 recombination and investigating the O2 excited states produced following the recombination. These measurements will provide key input for a quantitative understanding and reliable modeling of the atmospheres of the CO2 planets and their airglow. An excimer laser providing pulsed output at either 193 nm or 248 nm is employed to produce O atoms by dissociating carbon dioxide, nitrous oxide, or ozone. In an ambient-pressure background of CO2, O atoms recombine in a time scale of a few milliseconds. Detection of laser-induced fluorescence at 845 nm following two-photon excitation near 226 nm monitors the decay of the oxygen atom population. From the temporal evolution of the signal the recombination rate coefficient is extracted. Fluorescence spectroscopy is used to detect the products of O-atom recombination and subsequent relaxation in CO2. This work is supported by the US National Science Foundation’s (NSF) Planetary Astronomy Program. Rosanne Garcia’s participation was funded by the NSF Research Experiences for Undergraduates (REU) Program.

  20. Generation of atomic iodine via fluorine for chemical oxygen-iodine laser

    International Nuclear Information System (INIS)

    Jirasek, Vit; Spalek, Otomar; Censky, Miroslav; Pickova, Irena; Kodymova, Jarmila; Jakubec, Ivo

    2007-01-01

    A method of the chemical generation of atomic iodine for a chemical oxygen-iodine laser (COIL) using atomic fluorine as a reaction intermediate was studied experimentally. This method is based on the reaction between F 2 and NO providing F atoms, and the reaction of F with HI resulting in iodine atoms generation. Atomic iodine was produced with efficiency exceeding 40% relative to initial F 2 flow rate. This efficiency was nearly independent on pressure and total gas flow rate. The F atoms were stable in the reactor up to 2 ms. An optimum ratio of the reactants flow rates was F 2 :NO:HI = 1:1:1. A rate constant of the reaction of F 2 with HI was determined. The numerical modelling showed that remaining HI and IF were probably consumed in their mutual reaction. The reaction system was found suitable for employing in a generator of atomic iodine with its subsequent injection into a supersonic nozzle of a COIL

  1. Effects of atomic oxygen irradiation on the surface properties of phenolphthalein poly(ether sulfone)

    International Nuclear Information System (INIS)

    Pei Xianqiang; Li Yan; Wang Qihua; Sun Xiaojun

    2009-01-01

    To study the effects of low earth orbit environment on the surface properties of polymers, phenolphthalein poly(ether sulfone) (PES-C) blocks were irradiated by atomic oxygen in a ground-based simulation system. The surface properties of the pristine and irradiated blocks were studied by attenuated total-reflection FTIR (FTIR-ATR), X-ray photoelectron spectroscopy (XPS), scanning electron microscope (SEM). It was found that atomic oxygen irradiation induced the destruction of PES-C molecular chains, including the scission and oxidation of PES-C molecular chains, as evidenced by FTIR and XPS results. The scission of PES-C molecular chains decreased the relative concentration of C in the surface, while the oxidation increased the relative concentration of O in the surface. The changes in surface chemical structure and composition also changed the surface morphology of the block, which shifted from smooth structure before irradiation to 'carpet-like' structure after irradiation

  2. Synthesis of Environmentally Responsive Polymers by Atom Transfer Radical Polymerization: Generation of Reversible Hydrophilic and Hydrophobic Surfaces

    Directory of Open Access Journals (Sweden)

    Vikas Mittal

    2010-05-01

    Full Text Available Environmentally responsive poly(N-isopropylacrylamide brushes were grafted from the surface of polymer particles or flat surfaces in order to generate reversible hydrophilic and hydrophobic surfaces. The use of atom transfer radical polymerization was demonstrated for the grafting of polymer brushes as it allows efficient control on the amount of grafted polymer. The polymer particles were generated with or without surfactant in the emulsion polymerization and their surface could be modified with the atom transfer radical polymerization (ATRP initiator. The uniform functionalization of the surface with ATRP initiator was responsible for the uniform grafting of polymer brushes. The grafted brushes responded reversibly with changes in temperature indicating that the reversible responsive behavior could be translated to the particle surfaces. The particles were observed to adsorb and desorb protein and virus molecules by changing the temperatures below or higher than 32 °C. The initiator functionalized particles could also be adsorbed on the flat surfaces. The adsorption process also required optimization of the heat treatment conditions to form a uniform layer of the particles on the substrate. The grafted polymer brushes also responded to the changes in temperatures similar to the spherical particles studied through water droplets placed on the flat substrates.

  3. Poly(vinyl acetate-Based Block Copolymer/Clay Nanocomposites Prepared by In Situ Atom Transfer Radical Polymerization

    Directory of Open Access Journals (Sweden)

    M.A. Semsarzadeh

    2009-12-01

    Full Text Available Atom transfer radical polymerization of styrene (St and methyl methacrylate (MMA was performed at 90oC in the absence and presence of nanoclay (Cloisite 30B. Trichloromethyl-terminated poly(vinyl acetate telomerand CuCl/ PMDETA were used as a macroinitiator and catalyst system, respectively. The experimental results showed that the atom transfer radical polymerization of St and MMA in the absence or presence of nanoclay proceeds via a controlled/living mode. It was observed that nanoclay significantly enhances the homopolymerization rate of MMA, which was attributed to the activated conjugated C=C bond of MMA monomer via interaction between the carbonyl group of MMA monomer and the hydroxyl moiety (Al-O-H of nanoclay as well as the effect of nanoclay on the dynamic equilibrium between the active (macro radicals and dormant species.Homopolymerization rate of St (a non-coordinative monomer with nanoclay decreased slightly in the presence of nanoclay. This could be explained by insertion of a portion of macroinitiator into the clay galleries, where no sufficient St monomer exists due to the low compatibility or interaction of St monomer with nanoclay to react with the macroinitiator. The results obtained from XRD, TEM and TGA analyses were fully in agreement with the kinetic data. Structure of the poly(vinyl acetate-bpolystyrene nanocomposite was found to be a combination of stacking layers and exfoliated structures while poly(vinyl acetate-b-poly(methyl methacryale nanocomposite had an exfoliated structure. This difference in the structure of nanocomposites was attributed to the different capability of the monomers (styrene and methyl methacrylate to react with the hydroxyl moiety (Al-O-H of nanoclay.

  4. The mystery of gold's chemical activity: local bonding, morphology and reactivity of atomic oxygen.

    Science.gov (United States)

    Baker, Thomas A; Liu, Xiaoying; Friend, Cynthia M

    2011-01-07

    Recently, gold has been intensely studied as a catalyst for key synthetic reactions. Gold is an attractive catalyst because, surprisingly, it is highly active and very selective for partial oxidation processes suggesting promise for energy-efficient "green" chemistry. The underlying origin of the high activity of Au is a controversial subject since metallic gold is commonly thought to be inert. Herein, we establish that one origin of the high activity for gold catalysis is the extremely reactive nature of atomic oxygen bound in 3-fold coordination sites on metallic gold. This is the predominant form of O at low concentrations on the surface, which is a strong indication that it is most relevant to catalytic conditions. Atomic oxygen bound to metallic Au in 3-fold sites has high activity for CO oxidation, oxidation of olefins, and oxidative transformations of alcohols and amines. Among the factors identified as important in Au-O interaction are the morphology of the surface, the local binding site of oxygen, and the degree of order of the oxygen overlayer. In this Perspective, we present an overview of both theory and experiments that identify the reactive forms of O and their associated charge density distributions and bond strengths. We also analyze and model the release of Au atoms induced by O binding to the surface. This rough surface also has the potential for O(2) dissociation, which is a critical step if Au is to be activated catalytically. We further show the strong parallels between product distributions and reactivity for O-covered Au at low pressure (ultrahigh vacuum) and for nanoporous Au catalysts operating at atmospheric pressure as evidence that atomic O is the active species under working catalytic conditions when metallic Au is present. We briefly discuss the possible contributions of oxidants that may contain intact O-O bonds and of the Au-metal oxide support interface in Au catalysis. Finally, the challenges and future directions for fully

  5. Simulation of the Atomic and Electronic Structure of Oxygen Vacancies and Polyvacancies in ZrO2

    Science.gov (United States)

    Perevalov, T. V.

    2018-03-01

    Cubic, tetragonal, and monoclinic phases of zirconium oxide with oxygen vacancies and polyvacancies are studied by quantum chemical modeling of the atomic and electronic structure. It is demonstrated that an oxygen vacancy in ZrO2 may act as both an electron trap and a hole one. An electron added to the ZrO2 structure with an oxygen vacancy is distributed between two neighboring Zr atoms and is a bonding orbital by nature. It is advantageous for each subsequent O vacancy to form close to the already existing ones; notably, one Zr atom has no more than two removed O atoms related to it. Defect levels from oxygen polyvacancies are distributed in the bandgap with preferential localization in the vicinity of the oxygen monovacancy level.

  6. The Effect of Ash and Inorganic Pigment Fill on the Atomic Oxygen Erosion of Polymers and Paints (ISMSE-12)

    Science.gov (United States)

    Banks, Bruce A.; Simmons, Julie C.; de Groh, Kim K.; Miller, Sharon K.

    2012-01-01

    Low atomic oxygen fluence (below 1x10(exp 20) atoms/sq cm) exposure of polymers and paints that have a small ash content and/or inorganic pigment fill does not cause a significant difference in erosion yield compared to unfilled (neat) polymers or paints. However, if the ash and/or inorganic pigment content is increased, the surface population of the inorganic content will begin to occupy a significant fraction of the surface area as the atomic oxygen exposure increases because the ash is not volatile and remains as a loosely attached surface layer. This results in a reduction of the flux of atomic oxygen reacting with the polymer and a reduction in the rate of erosion of the polymer remaining. This paper presents the results of ground laboratory and low Earth orbital (LEO) investigations to evaluate the fluence dependence of atomic oxygen erosion yields of polymers and paints having inorganic fill content.

  7. Atomic Oxygen Erosion Yield Prediction for Spacecraft Polymers in Low Earth Orbit

    Science.gov (United States)

    Banks, Bruce A.; Backus, Jane A.; Manno, Michael V.; Waters, Deborah L.; Cameron, Kevin C.; deGroh, Kim K.

    2009-01-01

    The ability to predict the atomic oxygen erosion yield of polymers based on their chemistry and physical properties has been only partially successful because of a lack of reliable low Earth orbit (LEO) erosion yield data. Unfortunately, many of the early experiments did not utilize dehydrated mass loss measurements for erosion yield determination, and the resulting mass loss due to atomic oxygen exposure may have been compromised because samples were often not in consistent states of dehydration during the pre-flight and post-flight mass measurements. This is a particular problem for short duration mission exposures or low erosion yield materials. However, as a result of the retrieval of the Polymer Erosion and Contamination Experiment (PEACE) flown as part of the Materials International Space Station Experiment 2 (MISSE 2), the erosion yields of 38 polymers and pyrolytic graphite were accurately measured. The experiment was exposed to the LEO environment for 3.95 years from August 16, 2001 to July 30, 2005 and was successfully retrieved during a space walk on July 30, 2005 during Discovery s STS-114 Return to Flight mission. The 40 different materials tested (including Kapton H fluence witness samples) were selected specifically to represent a variety of polymers used in space as well as a wide variety of polymer chemical structures. The MISSE 2 PEACE Polymers experiment used carefully dehydrated mass measurements, as well as accurate density measurements to obtain accurate erosion yield data for high-fluence (8.43 1021 atoms/sq cm). The resulting data was used to develop an erosion yield predictive tool with a correlation coefficient of 0.895 and uncertainty of +/-6.3 10(exp -25)cu cm/atom. The predictive tool utilizes the chemical structures and physical properties of polymers to predict in-space atomic oxygen erosion yields. A predictive tool concept (September 2009 version) is presented which represents an improvement over an earlier (December 2008) version.

  8. Atomic Oxygen Erosion Yield Predictive Tool for Spacecraft Polymers in Low Earth Orbit

    Science.gov (United States)

    Bank, Bruce A.; de Groh, Kim K.; Backus, Jane A.

    2008-01-01

    A predictive tool was developed to estimate the low Earth orbit (LEO) atomic oxygen erosion yield of polymers based on the results of the Polymer Erosion and Contamination Experiment (PEACE) Polymers experiment flown as part of the Materials International Space Station Experiment 2 (MISSE 2). The MISSE 2 PEACE experiment accurately measured the erosion yield of a wide variety of polymers and pyrolytic graphite. The 40 different materials tested were selected specifically to represent a variety of polymers used in space as well as a wide variety of polymer chemical structures. The resulting erosion yield data was used to develop a predictive tool which utilizes chemical structure and physical properties of polymers that can be measured in ground laboratory testing to predict the in-space atomic oxygen erosion yield of a polymer. The properties include chemical structure, bonding information, density and ash content. The resulting predictive tool has a correlation coefficient of 0.914 when compared with actual MISSE 2 space data for 38 polymers and pyrolytic graphite. The intent of the predictive tool is to be able to make estimates of atomic oxygen erosion yields for new polymers without requiring expensive and time consumptive in-space testing.

  9. Influence of driving frequency on oxygen atom density in O2 radio frequency capacitively coupled plasma

    International Nuclear Information System (INIS)

    Kitajima, Takeshi; Noro, Kouichi; Nakano, Toshiki; Makabe, Toshiaki

    2004-01-01

    The influence of the driving frequency on the absolute oxygen atom density in an O 2 radio frequency (RF) capacitively coupled plasma (CCP) was investigated using vacuum ultraviolet absorption spectroscopy with pulse modulation of the main plasma. A low-power operation of a compact inductively coupled plasma light source was enabled to avoid the significant measurement errors caused by self-absorption in the light source. The pulse modulation of the main plasma enabled accurate absorption measurement for high plasma density conditions by eliminating background signals due to light emission from the main plasma. As for the effects of the driving frequency, the effect of VHF (100 MHz) drive on oxygen atom production was small because of the modest increase in plasma density of electronegative O 2 in contrast to the significant increase in electron density previously observed for electropositive Ar. The recombination coefficient of oxygen atoms on the electrode surface was obtained from a decay rate in the afterglow by comparison with a diffusion model, and it showed agreement with previously reported values for several electrode materials

  10. Atomic resolution chemical bond analysis of oxygen in La2CuO4

    Science.gov (United States)

    Haruta, M.; Nagai, T.; Lugg, N. R.; Neish, M. J.; Nagao, M.; Kurashima, K.; Allen, L. J.; Mizoguchi, T.; Kimoto, K.

    2013-08-01

    The distorted CuO6 octahedron in La2CuO4 was studied using aberration-corrected scanning transmission electron microscopy at atomic resolution. The near-edge structure in the oxygen K-edge electron energy-loss spectrum was recorded as a function of the position of the electron probe. After background subtraction, the measured spectrum image was processed using a recently developed inversion process to remove the mixing of signals on the atomic columns due to elastic and thermal scattering. The spectra were then compared with first-principles band structure calculations based on the local-density approximation plus on-site Coulomb repulsion (LDA + U) approach. In this article, we describe in detail not only anisotropic chemical bonding of the oxygen 2p state with the Cu 3d state but also with the Cu 4p and La 5d/4f states. Furthermore, it was found that buckling of the CuO2 plane was also detectable at the atomic resolution oxygen K-edge. Lastly, it was found that the effects of core-hole in the O K-edge were strongly dependent on the nature of the local chemical bonding, in particular, whether it is ionic or covalent.

  11. Chemical repair of trypsin-histidinyl radical

    International Nuclear Information System (INIS)

    Jovanovic, S.V.; Ruvarac, I.; Jankovic, I.; Josimovic, L.

    1991-01-01

    Oxyl radicals, such as hydroxyl, alkoxyl and peroxyl, react with biomolecules to produce bioradicals. Unless chemically repaired by suitable antioxidants, these bioradicals form stable products. This leads to loss of biological function of parent biomolecules with deleterious biological results, such as mutagenesis and cancer. Consequently, the understanding of the mechanisms of oxyl radical damage to biomolecules and chemical repair of such damage is crucial for the development of strategies for anticarcinogenesis and radioprotection. In this study the chemical repair of the histidinyl radical generated upon the trichloromethylperoxyl radical reaction with trypsin vas investigated by gamma radiolysis. The trypsin histidinyl radical is a resonance-stabilized heterocyclic free radical which was found to be unreactive with oxygen. The efficacy of the chemical repair of the trypsin-histidinyl radical by endogenous antioxidants which are electron donors (e.g. 5-hydroxytryptophan, uric acid) is compared to that of antioxidants which are H-atom donors (e. g. glutathione). 9 refs., 2 figs., 1 tab

  12. Characterization of atomic oxygen in a Hollow Cathode Radio-Frequency Plasma and study its efficiency

    International Nuclear Information System (INIS)

    Naddaf, M.; Saloum, S.

    2011-01-01

    The atomic oxygen (AO) generated in the remote oxygen plasma of the HCD-L300 source, has been fully diagnosed by various conventional techniques. The density of AO was found to vary from (1-10)x10 1 9 m - 3 depending on the operating conditions and parameters. The interaction of the oxygen plasma with silver and gold thin films is investigated by gravimetric analysis, scanning electron microscopy (SEM) and energy dispersive x-ray (EDX) spectroscopy. The effect of AO on surface wetting and energy of polymeric materials is also investigated by using contact angle measurements and analysis technique. From applied point of view, production of super hydrophobic Teflon surface and the significant enhancement in the surface free energy of polyimide and polyamide are considered the most important obtained results in the present work. (author)

  13. Formation of oxides and segregation of mobile atoms during SIMS profiling of Si with oxygen ions

    Energy Technology Data Exchange (ETDEWEB)

    Petravic, M; Williams, J S; Svensson, B G; Conway, M [Australian National Univ., Canberra, ACT (Australia). Research School of Physical Sciences

    1994-12-31

    An oxygen beam is commonly used in secondary ion mass spectroscopy (SIMS) analysis to enhance the ionization probability for positive secondary ions. It has been observed, however, that this technique produces in some cases a great degradation of depth resolution. The most pronounced effects have been found for impurities in silicon under oxygen bombardment at angles of incidence smaller than {approx} 30 deg from the surface normal. A new approach is described which involved broadening of SIMS profiles for some mobile atoms, such as Cu, Ni and Au, implanted into silicon. The anomalously large broadening is explained in terms of segregation at a SiO{sub 2}/Si interface formed during bombardment with oxygen at impact angles less than 30 deg. 2 refs., 1 tab., 4 figs.

  14. Formation of oxides and segregation of mobile atoms during SIMS profiling of Si with oxygen ions

    Energy Technology Data Exchange (ETDEWEB)

    Petravic, M.; Williams, J.S.; Svensson, B.G.; Conway, M. [Australian National Univ., Canberra, ACT (Australia). Research School of Physical Sciences

    1993-12-31

    An oxygen beam is commonly used in secondary ion mass spectroscopy (SIMS) analysis to enhance the ionization probability for positive secondary ions. It has been observed, however, that this technique produces in some cases a great degradation of depth resolution. The most pronounced effects have been found for impurities in silicon under oxygen bombardment at angles of incidence smaller than {approx} 30 deg from the surface normal. A new approach is described which involved broadening of SIMS profiles for some mobile atoms, such as Cu, Ni and Au, implanted into silicon. The anomalously large broadening is explained in terms of segregation at a SiO{sub 2}/Si interface formed during bombardment with oxygen at impact angles less than 30 deg. 2 refs., 1 tab., 4 figs.

  15. Study of atomic excitations in sputtering with targets partially covered with oxygen

    International Nuclear Information System (INIS)

    Weng, J.; Veje, E.

    1984-01-01

    We have bombarded pure, elemental targets of Be, B, Mg, Al, Si, Ti, and Au with 80 keV Ar + ions and studied excitation of sputtered atoms or ions under UHV conditions as well as with oxygen present at the target surface. The measurements on Mg, Al, Si, and Ti have been done at projectile incidence angles from 0 0 to 85 0 . Excitation probabilities for gold were found to be only very little influenced by oxygen, but for Be, B, Mg, Al, Si, and Ti, the excitation probabilities were in many, but not all, cases found to depend strongly on the oxygen pressure as well as on the beam current density. This indicates that the excitation mechanism is strongly dependent on the initial electronic conditions of the solid. (orig.)

  16. Determination of the neutral oxygen atom density in a plasma reactor loaded with metal samples

    Science.gov (United States)

    Mozetic, Miran; Cvelbar, Uros

    2009-08-01

    The density of neutral oxygen atoms was determined during processing of metal samples in a plasma reactor. The reactor was a Pyrex tube with an inner diameter of 11 cm and a length of 30 cm. Plasma was created by an inductively coupled radiofrequency generator operating at a frequency of 27.12 MHz and output power up to 500 W. The O density was measured at the edge of the glass tube with a copper fiber optics catalytic probe. The O atom density in the empty tube depended on pressure and was between 4 and 7 × 1021 m-3. The maximum O density was at a pressure of about 150 Pa, while the dissociation fraction of O2 molecules was maximal at the lowest pressure and decreased with increasing pressure. At about 300 Pa it dropped below 10%. The measurements were repeated in the chamber loaded with different metallic samples. In these cases, the density of oxygen atoms was lower than that in the empty chamber. The results were explained by a drain of O atoms caused by heterogeneous recombination on the samples.

  17. Oxidative damage of U937 human leukemic cells caused by hydroxyl radical results in singlet oxygen formation.

    Directory of Open Access Journals (Sweden)

    Marek Rác

    Full Text Available The exposure of human cells to oxidative stress leads to the oxidation of biomolecules such as lipids, proteins and nuclei acids. In this study, the oxidation of lipids, proteins and DNA was studied after the addition of hydrogen peroxide and Fenton reagent to cell suspension containing human leukemic monocyte lymphoma cell line U937. EPR spin-trapping data showed that the addition of hydrogen peroxide to the cell suspension formed hydroxyl radical via Fenton reaction mediated by endogenous metals. The malondialdehyde HPLC analysis showed no lipid peroxidation after the addition of hydrogen peroxide, whereas the Fenton reagent caused significant lipid peroxidation. The formation of protein carbonyls monitored by dot blot immunoassay and the DNA fragmentation measured by comet assay occurred after the addition of both hydrogen peroxide and Fenton reagent. Oxidative damage of biomolecules leads to the formation of singlet oxygen as conformed by EPR spin-trapping spectroscopy and the green fluorescence of singlet oxygen sensor green detected by confocal laser scanning microscopy. It is proposed here that singlet oxygen is formed by the decomposition of high-energy intermediates such as dioxetane or tetroxide formed by oxidative damage of biomolecules.

  18. High energy-intensity atomic oxygen beam source for low earth orbit materials degradation studies

    International Nuclear Information System (INIS)

    Cross, J.B.; Blais, N.C.

    1988-01-01

    A high intensity (10 19 O-atoms/s-sr) high energy (5 eV) source of oxygen atoms has been developed that produces a total fluence of 10 22 O-atoms/cm 2 in less than 100 hours of continuous operation at a distance of 15 cm from the source. The source employs a CW CO 2 laser sustained discharge to form a high temperature (15,000 K) plasma in the throat of a 0.3-mm diameter nozzle using 3--8 atmospheres of rare gas/O 2 mixtures. Visible and infrared photon flux levels of 1 watt/cm 2 have been measured 15 cm downstream of the source while vacuum UV (VUV) fluxes are comparable to that measured in low earth orbit. The reactions of atomic oxygen with kapton, Teflon, silver, and various coatings have been studied. The oxidation of kapton (reaction efficiency = 3 /times/ 10/sup /minus/24/ cm /+-/ 50%) has an activation energy of 0.8 Kcal/mole over the temperature range of 25/degree/C to 100/degree/C at a beam energy of 1.5 eV and produces low molecular weight gas phase reaction products (H 2 O, NO, CO 2 ). Teflon reacts with ∼0.1--0.2 efficiency to that of kapton at 25/degree/C and both surfaces show a rug-like texture after exposure to the O-atom beam. Angular scattering distribution measurements of O-atoms show a near cosine distribution from reactive surfaces indicating complete accommodation of the translational energy with the surface while a nonreactive surface (nickel oxide) shows specular-like scattering with 50% accommodation of the translational energy with the surface. A technique for simple on orbit chemical experiments using resistance measurements of coated silver strips is described. 9 figs

  19. The impact of oxygen availability on stress survival and radical formation of Bacillus cereus

    NARCIS (Netherlands)

    Mols, J.M.; Pier, I.; Zwietering, M.H.; Abee, T.

    2009-01-01

    Both the growth and stress survival of two model Bacillus cereus strains, ATCC 14579 and ATCC 10987, were tested in three different conditions varying in oxygen availability, i.e., aerobic, microaerobic and anaerobic conditions. Both B. cereus strains displayed highest growth rates and yields under

  20. Radiation-induced damage in E. coli B: The effect of superoxide radicals and molecular oxygen. Progress report, December 1, 1978--November 30, 1979

    International Nuclear Information System (INIS)

    Samuni, A.; Czapski, G.

    The roles of superoxide radicals and of molecular oxygen in the radiodamage of E. coli B suspended in dilute phosphate buffer were studied. The presence of high concentrations of polyethylene glycol in the γ-irradiated cell suspensions, had no effect on bacterial radiosensitivity. This indicates that the damage was primarily endogenous, i.e. originated intracellularly. Saturation of the cell suspensions with N 2 O doubled the radiosensitivity, thus indicating that OH radicals are responsible for the majority of the damage (indirect radiation effect). The presence of oxygen either in the absence or presence of N 2 O brought about roughly a three-fold increase in the radiosensitivity. Since in the presence of N 2 O all e - /sub aq/ are scavenged by the nitrous oxide rather than by oxygen, this shows that superoxide radicals play no role in the bacterial radiodamage. Our results substantiate the attribution of the oxygen effect to a direct interaction of O 2 with the hydroxyl-radical-damaged sites on vital biomolecules, and exclude any significant contribution of e - /sub aq/ and superoxide radicals to the cellular radiodamage

  1. Chemical reaction of atomic oxygen with evaporated films of copper, part 4

    Science.gov (United States)

    Fromhold, A. T.; Williams, J. R.

    1990-01-01

    Evaporated copper films were exposed to an atomic oxygen flux of 1.4 x 10(exp 17) atoms/sq cm per sec at temperatures in the range 285 to 375 F (140 to 191 C) for time intervals between 2 and 50 minutes. Rutherford backscattering spectroscopy (RBS) was used to determine the thickness of the oxide layers formed and the ratio of the number of copper to oxygen atoms in the layers. Oxide film thicknesses ranged from 50 to 3000 A (0.005 to 0.3 microns, or equivalently, 5 x 10(exp -9) to 3 x 10(exp -7); it was determined that the primary oxide phase was Cu2O. The growth law was found to be parabolic (L(t) varies as t(exp 1/2)), in which the oxide thickness L(t) increases as the square root of the exposure time t. The analysis of the data is consistent with either of the two parabolic growth laws. (The thin-film parabolic growth law is based on the assumption that the process is diffusion controlled, with the space charge within the growing oxide layer being negligible. The thick-film parabolic growth law is also based on a diffusion controlled process, but space-charge neutrality prevails locally within very thick oxides.) In the absence of a voltage measurement across the growing oxide, a distinction between the two mechanisms cannot be made, nor can growth by the diffusion of neutral atomic oxygen be entirely ruled out. The activation energy for the reaction is on the order of 1.1 eV (1.76 x 10(exp -19) joule, or equivalently, 25.3 kcal/mole).

  2. Automatic measuring device for atomic oxygen concentrations (1962); Dispositif de mesure automatique de concentrations d'oxygene atomique (1962)

    Energy Technology Data Exchange (ETDEWEB)

    Weill, J; Deiss, M; Mercier, R [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1962-07-01

    Within the framework of the activities of the Autonomous Reactor Electronics Section we have developed a device, which renders automatic one type of measurement carried out in the Physical Chemistry Department at the Saclay Research Centre. We define here: - the physico-chemical principle of the apparatus which is adapted to the measurement of atomic oxygen concentrations; - the physical principle of the automatic measurement; - the properties, performance, constitution, use and maintenance of the automatic measurement device. It is concluded that the principle of the automatic device, whose tests have confirmed the estimation of the theoretical performance, could usefully be adapted to other types of measurement. (authors) [French] Dans le cadre des activites de la Section Autonome d'Electronique des Reacteurs, il a ete realise et mis au point un dispositif permettant de rendre automatique un type de mesures effectuees au Departement de Physico-Chimie du C.E.N. SACLAY. On definit ici: - le principe physico-chimique de l'appareillage, adapte a la mesure de concentrations de l'oxygene atomique; - le principe physique de la mesure automatique; - les qualites, performances, constitution, utilisation, et maintenance du dispositif de mesure automatique. Il est porte en conclusion, que le principe du dispositif automatique realise, dont les essais ont sensiblement confirme l'evaluation des performances theoriques, pourrait etre utilement adapte a d'autres types de mesures courantes. (auteurs)

  3. Carp head kidney leukocytes display different patterns of oxygen radical production after stimulation with PAMPs and DAMPs

    DEFF Research Database (Denmark)

    Jiménez, Natalia Ivonne Vera; Nielsen, Michael Engelbrecht

    2013-01-01

    . Consistent with a pathogen eradication strategy, ROS responses to PAMP stimulation (β-glucan) was fast, vigorous and highly dominated by production of superoxide anion. In contrast, stimulation with DAMPs led to a slow, subtle but long-lasting production of oxygen radicals dominated by hydrogen peroxide....... Using an in vitro model of scratch-wounded CCB fibroblast cell cultures and a novel PhotoID proliferation assay, stimulation with low and continuous levels of hydrogen peroxide (5μM) led to a slight increase in the percentage of wound recovery and thus promoted wound closure. In contrast, high doses...... and thereby potential tissue damage. Direct in vitro stimulation with β-glucans did not impact fibroblast scratch-wound recovery, which further suggests that interaction with tissue-resident leukocytes or other components of the fish immune system are required to induce fibroblast proliferation and thus...

  4. Adsorption of atomic oxygen on PdAg/Pd(111) surface alloys and coadsorption of CO

    Energy Technology Data Exchange (ETDEWEB)

    Farkas, Arnold P. [Institute of Surface Chemistry and Catalysis, Ulm University, D-89069 Ulm (Germany); Reaction Kinetics Research Group, University of Szeged, Chemical Research Center of the Hungarian Academy of Sciences, H-6720 Szeged (Hungary); Bansmann, Joachim; Diemant, Thomas; Behm, R. Juergen [Institute of Surface Chemistry and Catalysis, Ulm University, D-89069 Ulm (Germany)

    2011-07-01

    The interaction of dissociated oxygen with structurally well-defined PdAg/Pd(111) surface alloys and the coadsorption of CO was studied by high resolution electron energy loss spectroscopy (HREELS) and temperature-programmed desorption (TPD). After oxygen saturation of the non-modified Pd(111) surface at RT, we observed the formation of a prominent peak in the HREEL spectra at 60 meV corresponding to the perpendicular vibration of oxygen atoms adsorbed in threefold hollow sites. Deposition of small Ag amounts does not change the signal intensity of this peak; it decreases only above 20% Ag. Beyond this Ag content, the peak intensity steeply declines and disappears at around 55-60% Ag. CO coadsorption on the oxygen pre-covered surfaces at 120 K leads to the formation of additional features in HREELS. For a surface alloy with 29% Ag, three loss features due to CO adsorption in on-top, bridge, and threefold-hollow sites can be discriminated already after the lowest CO exposure. Annealing of the co-adsorbed layer to 200 K triggers a decrease of the oxygen concentration due to CO{sub 2} formation. These findings are corroborated by TPD spectra of the CO desorption and CO{sub 2} production.

  5. Degradation of methyl and ethyl mercury into inorganic mercury by other reactive oxygen species besides hydroxyl radical

    Energy Technology Data Exchange (ETDEWEB)

    Suda, Ikuo; Takahashi, Hitoshi (Kumamoto Univ. Medical School (Japan). Inst. for Medical Immunology)

    1992-01-01

    Degradation of methyl mercury (MeHg) and ethyl Hg (EtHg) with reactive oxygens was studied in vitro by using peroxidase-hydrogen peroxide (H{sub 2}O{sub 2})-halide and rose bengal-ultraviolet light A systems. For this purpose, the direct determination method for inorganic Hg was employed. Both systems could effectively degrade EtHg, and MeHg to some extent. Degradation of MeHg and EtHg with the myeloperoxidase (MPO)-H{sub 2}O{sub 2}-chloride system was inhibited by MPO inhibitors (cyanide and azide), catalase, hypochlorous acid (HOCl) scavengers (glycine, alanine, serine and taurine), 1,4-diazabicyclo(2,2,2)octane and 2,5-dimethylfuran, but not by hydroxyl radical scavengers (ethanol and mannitol). Iodide was more effective than chloride as the halide component. Lactoperoxidase (LPO) could substitute for MPO in the iodide, but not the chloride system. With MPO-H{sub 2}O{sub 2}-chloride, MPO-H{sub 2}O{sub 2}-iodide and LPO-H{sub 2}O{sub 2}-iodide systems, we observed the increased degradation of EtHg in deuterium oxide (D{sub 2}O) medium better than that in H{sub 2}O medium. The D{sub 2}O effect upon MeHg degradation was extremely weak. These results suggested that HOCl (or HOI) might be also capable of degrading MeHg and EtHg, besides the hydroxyl radical already reported by us. Singlet oxygen could degrade EtHg but not MeHg. (orig.).

  6. Reactivity of chemisorbed oxygen atoms and their catalytic consequences during CH4-O2 catalysis on supported Pt clusters.

    Science.gov (United States)

    Chin, Ya-Huei Cathy; Buda, Corneliu; Neurock, Matthew; Iglesia, Enrique

    2011-10-12

    Kinetic and isotopic data and density functional theory treatments provide evidence for the elementary steps and the active site requirements involved in the four distinct kinetic regimes observed during CH(4) oxidation reactions using O(2), H(2)O, or CO(2) as oxidants on Pt clusters. These four regimes exhibit distinct rate equations because of the involvement of different kinetically relevant steps, predominant adsorbed species, and rate and equilibrium constants for different elementary steps. Transitions among regimes occur as chemisorbed oxygen (O*) coverages change on Pt clusters. O* coverages are given, in turn, by a virtual O(2) pressure, which represents the pressure that would give the prevalent steady-state O* coverages if their adsorption-desorption equilibrium was maintained. The virtual O(2) pressure acts as a surrogate for oxygen chemical potentials at catalytic surfaces and reflects the kinetic coupling between C-H and O═O activation steps. O* coverages and virtual pressures depend on O(2) pressure when O(2) activation is equilibrated and on O(2)/CH(4) ratios when this step becomes irreversible as a result of fast scavenging of O* by CH(4)-derived intermediates. In three of these kinetic regimes, C-H bond activation is the sole kinetically relevant step, but occurs on different active sites, which evolve from oxygen-oxygen (O*-O*), to oxygen-oxygen vacancy (O*-*), and to vacancy-vacancy (*-*) site pairs as O* coverages decrease. On O*-saturated cluster surfaces, O*-O* site pairs activate C-H bonds in CH(4) via homolytic hydrogen abstraction steps that form CH(3) groups with significant radical character and weak interactions with the surface at the transition state. In this regime, rates depend linearly on CH(4) pressure but are independent of O(2) pressure. The observed normal CH(4)/CD(4) kinetic isotope effects are consistent with the kinetic-relevance of C-H bond activation; identical (16)O(2)-(18)O(2) isotopic exchange rates in the presence or

  7. Hydrophilization of Poly(ether ether ketone) Films by Surface-initiated Atom Transfer Radical Polymerization

    DEFF Research Database (Denmark)

    Fristrup, Charlotte Juel; Eskimergen, Rüya; Burkrinsky, J.T.

    2008-01-01

    and confirmed by ATR FTIR, water contact ang;le, and Thermal Gravimetric Analysis (TGA). The surface topography was evaluated by "Atomic Force Microscopy (AFM). X-ray Photoelectron Spectroscopy (XPS) has been used to investigate the degree of functionalization. The performed modification allowed for successful...

  8. Atomic Oxygen Abundance in Molecular Clouds: Absorption Toward Sagittarius B2

    Science.gov (United States)

    Lis, D. C.; Keene, Jocelyn; Phillips, T. G.; Schilke, P.; Werner, M. W.; Zmuidzinas, J.

    2001-01-01

    We have obtained high-resolution (approximately 35 km/s) spectra toward the molecular cloud Sgr B2 at 63 micrometers, the wavelength of the ground-state fine-structure line of atomic oxygen (O(I)), using the ISO-LWS instrument. Four separate velocity components are seen in the deconvolved spectrum, in absorption against the dust continuum emission of Sgr B2. Three of these components, corresponding to foreground clouds, are used to study the O(I) content of the cool molecular gas along the line of sight. In principle, the atomic oxygen that produces a particular velocity component could exist in any, or all, of three physically distinct regions: inside a dense molecular cloud, in the UV illuminated surface layer (PDR) of a cloud, and in an atomic (H(I)) gas halo. For each of the three foreground clouds, we estimate, and subtract from the observed O(I) column density, the oxygen content of the H(I) halo gas, by scaling from a published high-resolution 21 cm spectrum. We find that the remaining O(I) column density is correlated with the observed (13)CO column density. From the slope of this correlation, an average [O(I)]/[(13)CO] ratio of 270 +/- 120 (3-sigma) is derived, which corresponds to [O(I)]/[(13)CO] = 9 for a CO to (13)CO abundance ratio of 30. Assuming a (13)CO abundance of 1x10(exp -6) with respect to H nuclei, we derive an atomic oxygen abundance of 2.7x10(exp -4) in the dense gas phase, corresponding to a 15% oxygen depletion compared to the diffuse ISM in our Galactic neighborhood. The presence of multiple, spectrally resolved velocity components in the Sgr B2 absorption spectrum allows, for the first time, a direct determination of the PDR contribution to the O(I) column density. The PDR regions should contain O(I) but not (13)CO, and would thus be expected to produce an offset in the O(I)-(13)CO correlation. Our data do not show such an offset, suggesting that within our beam O(I) is spatially coexistent with the molecular gas, as traced by (13)CO

  9. Irradiation induced defects containing oxygen atoms in germanium crystal as studied by deep level transient spectroscopy

    International Nuclear Information System (INIS)

    Fukuoka, Noboru; Kambe, Yoshiyuki; Saito, Haruo; Matsuda, Koji.

    1984-05-01

    Deep level transient spectroscopy was applied to the electron trapping levels which are associated with the irradiation induced lattice defects in germanium crystals. The germanium crystals used in the study were doped with oxygen, antimony or arsenic and the defects were formed by electron irradiation of 1.5MeV or 10MeV. The nature of so called ''thermal defect'' formed by heat treatment at about 670K was also studied. The trapping levels at Esub(c)-0.13eV, Esub(c)-0.25eV and Esub(c)-0.29eV were found to be associated with defects containing oxygen atoms. From the experimental results the Esub(c)-0.25eV level was attributed to the germanium A-center (interstitial oxygen atom-vacancy pair). Another defect associated with the 715cm -1 infrared absorption band was found to have a trapping level at the same position at Esub(c)-0.25eV. The Esub(c)-0.23eV and Esub(c)-0.1eV levels were revealed to be associated with thermal donors formed by heat treatment at about 670K. Additional two peaks (levels) were observed in the DLTS spectrum. The annealing behavior of the levels suggests that the thermal donors originate from not a single type but several types of defects. (author)

  10. Carbon-hydrogen defects with a neighboring oxygen atom in n-type Si

    Science.gov (United States)

    Gwozdz, K.; Stübner, R.; Kolkovsky, Vl.; Weber, J.

    2017-07-01

    We report on the electrical activation of neutral carbon-oxygen complexes in Si by wet-chemical etching at room temperature. Two deep levels, E65 and E75, are observed by deep level transient spectroscopy in n-type Czochralski Si. The activation enthalpies of E65 and E75 are obtained as EC-0.11 eV (E65) and EC-0.13 eV (E75). The electric field dependence of their emission rates relates both levels to single acceptor states. From the analysis of the depth profiles, we conclude that the levels belong to two different defects, which contain only one hydrogen atom. A configuration is proposed, where the CH1BC defect, with hydrogen in the bond-centered position between neighboring C and Si atoms, is disturbed by interstitial oxygen in the second nearest neighbor position to substitutional carbon. The significant reduction of the CH1BC concentration in samples with high oxygen concentrations limits the use of this defect for the determination of low concentrations of substitutional carbon in Si samples.

  11. On I(5577 Å and I (7620 Å auroral emissions and atomic oxygen densities

    Directory of Open Access Journals (Sweden)

    R. L. Gattinger

    1996-07-01

    Full Text Available A model of auroral electron deposition processes has been developed using Monte Carlo techniques to simulate electron transport and energy loss. The computed differential electron flux and pitch angle were compared with in situ auroral observations to provide a check on the accuracy of the model. As part of the energy loss process, a tally was kept of electronic excitation and ionization of the important atomic and molecular states. The optical emission rates from these excited states were computed and compared with auroral observations of η(3914 Å, η(5577 Å, η(7620 Å and η(N2VK. In particular, the roles played by energy transfer from N2(A3Σ+u and by other processes in the excitation of O(1S and O2(b1Σ+g were investigated in detail. It is concluded that the N2(A3Σ+u mechanism is dominant for the production of OI(5577 Å in the peak emission region of normal aurora, although the production efficiency is much smaller than the measured laboratory value; above 150 km electron impact on atomic oxygen is dominant. Atomic oxygen densities in the range of 0.75±0.25 MSIS-86 [O] were derived from the optical comparisons for auroral latitudes in mid-winter for various levels of solar and magnetic activity.

  12. Surface-Initiated Atom Transfer Radical Polymerization and Electrografting Technique as a Means For Attaining Tailor-Made Polymer Coatings

    DEFF Research Database (Denmark)

    Chernyy, Sergey

    2012-01-01

    strategies for initiator grafting, physicochemical properties of polymer brushes and basic principles of quartz crystal microbalance technique (QCM) are discussed. In Chapter 2 various ATRP conditions are probed. The effects of solvent polarity, monomer concentration, initiator surface density, ligand nature......Atom transfer radical polymerization initiated from a surface of various substrates (SI-ATRP) has become a progressively popular technique for obtaining thin polymer films with predetermined properties. The present work addresses the main features of SI-ATRP with respect to the controllability...... and temperature on the kinetics of methyl methacrylate polymerization are elucidated. The strategy was based on the observation of dry polymer thickness versus time evolution by means of ellipsometry, profilometry and IR spectroscopy. An alternative approach, constituting Chapter 3, was based on optimization...

  13. Surface-Initiated Graft Atom Transfer Radical Polymerization of Methyl Methacrylate from Chitin Nanofiber Macroinitiator under Dispersion Conditions

    Directory of Open Access Journals (Sweden)

    Ryo Endo

    2015-08-01

    Full Text Available Surface-initiated graft atom transfer radical polymerization (ATRP of methyl methacrylate (MMA from self-assembled chitin nanofibers (CNFs was performed under dispersion conditions. Self-assembled CNFs were initially prepared by regeneration from a chitin ion gel with 1-allyl-3-methylimidazolium bromide using methanol; the product was then converted into the chitin nanofiber macroinitiator by reaction with α-bromoisobutyryl bromide in a dispersion containing N,N-dimethylformamide. Surface-initiated graft ATRP of MMA from the initiating sites on the CNFs was subsequently carried out under dispersion conditions, followed by filtration to obtain the CNF-graft-polyMMA film. Analysis of the product confirmed the occurrence of the graft ATRP on the surface of the CNFs.

  14. Visible Light-Induced Metal Free Surface Initiated Atom Transfer Radical Polymerization of Methyl Methacrylate on SBA-15

    Directory of Open Access Journals (Sweden)

    Liang Ma

    2017-02-01

    Full Text Available Surface-initiated atom transfer radical polymerization (SI-ATRP is one of the most versatile techniques to modify the surface properties of materials. Recent developed metal-free SI-ATRP makes such techniques more widely applicable. Herein photo-induced metal-free SI-ATRP of methacrylates, such as methyl methacrylate, N-isopropanyl acrylamide, and N,N-dimethylaminoethyl methacrylate, on the surface of SBA-15 was reported to fabricate organic-inorganic hybrid materials. A SBA-15-based polymeric composite with an adjustable graft ratio was obtained. The structure evolution during the SI-ATRP modification of SBA-15 was monitored and verified by FT-IR, XPS, TGA, BET, and TEM. The obtained polymeric composite showed enhanced adsorption ability for the model compound toluene in aqueous conditions. This procedure provides a low-cost, readily available, and easy modification method to synthesize polymeric composites without the contamination of metal.

  15. Crystalline TiO2 grafted with poly(2-methacryloyloxyethyl phosphorylcholine) via surface-initiated atom-transfer radical polymerization

    International Nuclear Information System (INIS)

    Zhao Yuancong; Tu Qiufen; Wang Jin; Huang Qiongjian; Huang Nan

    2010-01-01

    Crystalline TiO 2 films were prepared by unbalanced magnetron sputtering and the structure was confirmed by XRD. An organic layer of 11-hydroxyundecylphosphonic acid (HUPA) was prepared on the TiO 2 films by self-assembling, and the HUPA on TiO 2 films was confirmed by FTIR analysis. Simultaneously, hydroxyl groups were introduced in the phosphonic acid molecules to provide a functionality for further chemical modification. 2-Methacryloyloxyethyl phosphorylcholine (MPC), a biomimetic monomer, was chemically grafted on the HUPA surfaces at room temperature by surface-initiated atom-transfer radical polymerization. The surface characters of TiO 2 films modified by poly-MPC were confirmed by FTIR, XPS and SEM analysis. Platelet adhesion experiment revealed that poly-MPC modified surface was effective to inhibit platelet adhesion in vitro.

  16. Crystalline TiO 2 grafted with poly(2-methacryloyloxyethyl phosphorylcholine) via surface-initiated atom-transfer radical polymerization

    Science.gov (United States)

    Zhao, Yuancong; Tu, Qiufen; Wang, Jin; Huang, Qiongjian; Huang, Nan

    2010-12-01

    Crystalline TiO 2 films were prepared by unbalanced magnetron sputtering and the structure was confirmed by XRD. An organic layer of 11-hydroxyundecylphosphonic acid (HUPA) was prepared on the TiO 2 films by self-assembling, and the HUPA on TiO 2 films was confirmed by FTIR analysis. Simultaneously, hydroxyl groups were introduced in the phosphonic acid molecules to provide a functionality for further chemical modification. 2-Methacryloyloxyethyl phosphorylcholine (MPC), a biomimetic monomer, was chemically grafted on the HUPA surfaces at room temperature by surface-initiated atom-transfer radical polymerization. The surface characters of TiO 2 films modified by poly-MPC were confirmed by FTIR, XPS and SEM analysis. Platelet adhesion experiment revealed that poly-MPC modified surface was effective to inhibit platelet adhesion in vitro.

  17. Activators generated by electron transfer for atom transfer radical polymerization of styrene in the presence of mesoporous silica nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Khezri, Khezrollah, E-mail: kh.khezri@ut.ac.ir [School of Chemistry, University College of Science, University of Tehran, PO Box 14155-6455, Tehran (Iran, Islamic Republic of); Roghani-Mamaqani, Hossein [Department of Polymer Engineering, Sahand University of Technology, PO Box 51335-1996, Tabriz (Iran, Islamic Republic of)

    2014-11-15

    Graphical abstract: Effect of mesoporous silica nanoparticles (MCM-41) on the activator generated by electron transfer for atom transfer radical polymerization (AGET ATRP) is investigated. Decrement of conversion and number average molecular weight and also increment of polydispersity index (PDI) values are three main results of addition of MCM-41 nanoparticles. Incorporation of MCM-41 nanoparticles in the polystyrene matrix can clearly increase thermal stability and decrease glass transition temperature of the nanocomposites. - Highlights: • Spherical morphology, hexagonal structure, and high surface area with regular pore diameters of the synthesized MCM-41 nanoparticles are examined. • AGET ATRP of styrene in the presence of MCM-41 nanoparticles is performed. • Effect of MCM-41 nanoparticles addition on the polymerization rate, conversion and molecular weights of the products are discussed. • Improvement in thermal stability of the nanocomposites and decreasing T{sub g} values was also observed by incorporation of MCM-41 nanoparticles. - Abstract: Activator generated by electron transfer for atom transfer radical polymerization was employed to synthesize well-defined mesoporous silica nanoparticles/polystyrene composites. Inherent features of spherical mesoporous silica nanoparticles were evaluated by nitrogen adsorption/desorption isotherm, X-ray diffraction and scanning electron microscopy analysis techniques. Conversion and molecular weight evaluations were carried out using gas and size exclusion chromatography respectively. By the addition of only 3 wt% mesoporous silica nanoparticles, conversion decreases from 81 to 58%. Similarly, number average molecular weight decreases from 17,116 to 12,798 g mol{sup −1}. However, polydispersity index (PDI) values increases from 1.24 to 1.58. A peak around 4.1–4.2 ppm at proton nuclear magnetic resonance spectroscopy results clearly confirms the living nature of the polymerization. Thermogravimetric

  18. Cardiomyocyte hypertrophy induced by Endonuclease G deficiency requires reactive oxygen radicals accumulation and is inhibitable by the micropeptide humanin.

    Science.gov (United States)

    Blasco, Natividad; Cámara, Yolanda; Núñez, Estefanía; Beà, Aida; Barés, Gisel; Forné, Carles; Ruíz-Meana, Marisol; Girón, Cristina; Barba, Ignasi; García-Arumí, Elena; García-Dorado, David; Vázquez, Jesús; Martí, Ramon; Llovera, Marta; Sanchis, Daniel

    2018-06-01

    The endonuclease G gene (Endog), which codes for a mitochondrial nuclease, was identified as a determinant of cardiac hypertrophy. How ENDOG controls cardiomyocyte growth is still unknown. Thus, we aimed at finding the link between ENDOG activity and cardiomyocyte growth. Endog deficiency induced reactive oxygen species (ROS) accumulation and abnormal growth in neonatal rodent cardiomyocytes, altering the AKT-GSK3β and Class-II histone deacethylases (HDAC) signal transduction pathways. These effects were blocked by ROS scavengers. Lack of ENDOG reduced mitochondrial DNA (mtDNA) replication independently of ROS accumulation. Because mtDNA encodes several subunits of the mitochondrial electron transport chain, whose activity is an important source of cellular ROS, we investigated whether Endog deficiency compromised the expression and activity of the respiratory chain complexes but found no changes in these parameters nor in ATP content. MtDNA also codes for humanin, a micropeptide with possible metabolic functions. Nanomolar concentrations of synthetic humanin restored normal ROS levels and cell size in Endog-deficient cardiomyocytes. These results support the involvement of redox signaling in the control of cardiomyocyte growth by ENDOG and suggest a pathway relating mtDNA content to the regulation of cell growth probably involving humanin, which prevents reactive oxygen radicals accumulation and hypertrophy induced by Endog deficiency. Copyright © 2018 The Authors. Published by Elsevier B.V. All rights reserved.

  19. Computer simulations of an oxygen inductively coupled plasma used for plasma-assisted atomic layer deposition

    International Nuclear Information System (INIS)

    Tinck, S; Bogaerts, A

    2011-01-01

    In this paper, an O 2 inductively coupled plasma used for plasma enhanced atomic layer deposition of Al 2 O 3 thin films is investigated by means of modeling. This work intends to provide more information about basic plasma properties such as species densities and species fluxes to the substrate as a function of power and pressure, which might be hard to measure experimentally. For this purpose, a hybrid model developed by Kushner et al is applied to calculate the plasma characteristics in the reactor volume for different chamber pressures ranging from 1 to 10 mTorr and different coil powers ranging from 50 to 500 W. Density profiles of the various oxygen containing plasma species are reported as well as fluxes to the substrate under various operating conditions. Furthermore, different orientations of the substrate, which can be placed vertically or horizontally in the reactor, are taken into account. In addition, special attention is paid to the recombination process of atomic oxygen on the different reactor walls under the stated operating conditions. From this work it can be concluded that the plasma properties change significantly in different locations of the reactor. The plasma density near the cylindrical coil is high, while it is almost negligible in the neighborhood of the substrate. Ion and excited species fluxes to the substrate are found to be very low and negligible. Finally, the orientation of the substrate has a minor effect on the flux of O 2 , while it has a significant effect on the flux of O. In the horizontal configuration, the flux of atomic oxygen can be up to one order of magnitude lower than in the vertical configuration.

  20. Electrochemical Water Oxidation and Stereoselective Oxygen Atom Transfer Mediated by a Copper Complex.

    Science.gov (United States)

    Kafentzi, Maria-Chrysanthi; Papadakis, Raffaello; Gennarini, Federica; Kochem, Amélie; Iranzo, Olga; Le Mest, Yves; Le Poul, Nicolas; Tron, Thierry; Faure, Bruno; Simaan, A Jalila; Réglier, Marius

    2018-04-06

    Water oxidation by copper-based complexes to form dioxygen has attracted attention in recent years, with the aim of developing efficient and cheap catalysts for chemical energy storage. In addition, high-valent metal-oxo species produced by the oxidation of metal complexes in the presence of water can be used to achieve substrate oxygenation with the use of H 2 O as an oxygen source. To date, this strategy has not been reported for copper complexes. Herein, a copper(II) complex, [(RPY2)Cu(OTf) 2 ] (RPY2=N-substituted bis[2-pyridyl(ethylamine)] ligands; R=indane; OTf=triflate), is used. This complex, which contains an oxidizable substrate moiety (indane), is used as a tool to monitor an intramolecular oxygen atom transfer reaction. Electrochemical properties were investigated and, upon electrolysis at 1.30 V versus a normal hydrogen electrode (NHE), both dioxygen production and oxygenation of the indane moiety were observed. The ligand was oxidized in a highly diastereoselective manner, which indicated that the observed reactivity was mediated by metal-centered reactive species. The pH dependence of the reactivity was monitored and correlated with speciation deduced from different techniques, ranging from potentiometric titrations to spectroscopic studies and DFT calculations. Water oxidation for dioxygen production occurs at neutral pH and is probably mediated by the oxidation of a mononuclear copper(II) precursor. It is achieved with a rather low overpotential (280 mV at pH 7), although with limited efficiency. On the other hand, oxygenation is maximum at pH 8-8.5 and is probably mediated by the electrochemical oxidation of an antiferromagnetically coupled dinuclear bis(μ-hydroxo) copper(II) precursor. This constitutes the first example of copper-centered oxidative water activation for a selective oxygenation reaction. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Femtosecond, two-photon laser-induced-fluorescence imaging of atomic oxygen in an atmospheric-pressure plasma jet

    Science.gov (United States)

    Schmidt, Jacob B.; Sands, Brian L.; Kulatilaka, Waruna D.; Roy, Sukesh; Scofield, James; Gord, James R.

    2015-06-01

    Femtosecond, two-photon-absorption laser-induced-fluorescence (fs-TALIF) spectroscopy is employed to measure space- and time-resolved atomic-oxygen distributions in a nanosecond, repetitively pulsed, externally grounded, atmospheric-pressure plasma jet flowing helium with a variable oxygen admixture. The high-peak-intensity, low-average-energy femtosecond pulses result in increased TALIF signal with reduced photolytic inferences. This allows 2D imaging of absolute atomic-oxygen number densities ranging from 5.8   ×   1015 to 2.0   ×   1012cm-3 using a cooled CCD with an external intensifier. Xenon is used for signal and imaging-system calibrations to quantify the atomic-oxygen fluorescence signal. Initial results highlight a transition in discharge morphology from annular to filamentary, corresponding with a change in plasma chemistry from ozone to atomic oxygen production, as the concentration of oxygen in the feed gas is changed at a fixed voltage-pulse-repetition rate. In this configuration, significant concentrations of reactive oxygen species may be remotely generated by sustaining an active discharge beyond the confines of the dielectric capillary, which may benefit applications that require large concentrations of reactive oxygen species such as material processing or biomedical devices.

  2. Atomic scale study of the chemistry of oxygen, hydrogen and water at SiC surfaces

    International Nuclear Information System (INIS)

    Amy, Fabrice

    2007-01-01

    Understanding the achievable degree of homogeneity and the effect of surface structure on semiconductor surface chemistry is both academically challenging and of great practical interest to enable fabrication of future generations of devices. In that respect, silicon terminated SiC surfaces such as the cubic 3C-SiC(1 0 0) 3 x 2 and the hexagonal 6H-SiC(0 0 0 1) 3 x 3 are of special interest since they give a unique opportunity to investigate the role of surface morphology on oxygen or hydrogen incorporation into the surface. In contrast to silicon, the subsurface structure plays a major role in the reactivity, leading to unexpected consequences such as the initial oxidation starting several atomic planes below the top surface or the surface metallization by atomic hydrogen. (review article)

  3. Atomic oxygen adsorption and its effect on the oxidation behaviour of ZrB2-ZrC-SiC in air

    International Nuclear Information System (INIS)

    Gao Dong; Zhang Yue; Xu Chunlai; Song Yang; Shi Xiaobin

    2011-01-01

    Research highlights: → Atomic oxygen was adsorbed on the surface of ZrB 2 -ZrC-SiC ceramics. → Atomic oxygen was preferred reacted with borides according to XPS spectra. → The atomic oxygen adsorption is detrimental to the oxidation resistance. → The porosity should be the major reason which provides diffusion path for the atomic oxygen. → The structure evolution of the ceramics during oxidation is analyzed. - Abstract: Atomic oxygen is adsorbed on the surface of the hot-pressed ZrB 2 -ZrC-SiC ceramic composites, and then the ceramic composites are oxidized in air up to 1500 deg. C with the purpose of clarifying the effect of atomic oxygen adsorption on the oxidation behaviour of the ceramic composites. The XPS spectra are employed to identify the adsorption mechanism of atomic oxygen on the surface of the ceramic composites, and the formation of O-B, O-Zr, and O-Si bonds indicates that atomic oxygen is chemically adsorbed on the surface of the ceramic. In addition, atomic oxygen is preferred to be adsorbed on the surface of borides according to the Zr 3d core level spectrum. On the other hand, the atomic oxygen adsorption is detrimental to the oxidation resistance according to experimental results, and the porosity of the ceramic should be the major reason which provides diffusion path for the atomic oxygen. Furthermore, the structure evolution of the ceramic composites during oxidation process is analyzed.

  4. Atom-radical reaction dynamics of O(3P)+C3H5→C3H4+OH: Nascent rovibrational state distributions of product OH

    Science.gov (United States)

    Park, Jong-Ho; Lee, Hohjai; Kwon, Han-Cheol; Kim, Hee-Kyung; Choi, Young-Sang; Choi, Jong-Ho

    2002-08-01

    The reaction dynamics of ground-state atomic oxygen [O(3P)] with allyl radicals (C3H5) has been investigated by applying a combination of crossed beams and laser induced fluorescence techniques. The reactants O(3P) and C3H5 were produced by the photodissociation of NO2 and the supersonic flash pyrolysis of precursor allyl iodide, respectively. A new exothermic channel of O(3P)+C3H5→C3H4+OH was observed and the nascent internal state distributions of the product OH (X 2Π:υ″=0,1) showed substantial bimodal internal excitations of the low- and high-N″ components without Λ-doublet and spin-orbit propensities in the ground and first excited vibrational states. With the aid of the CBS-QB3 level of ab initio theory and Rice-Ramsperger-Kassel-Marcus calculations, it is predicted that on the lowest doublet potential energy surface the major reaction channel of O(3P) with C3H5 is the formation of acrolein (CH2CHCHO)+H, which is consistent with the previous bulk kinetic experiments performed by Gutman et al. [J. Phys. Chem. 94, 3652 (1990)]. The counterpart C3H4 of the probed OH product in the title reaction is calculated to be allene after taking into account the factors of reaction enthalpy, barrier height and the number of intermediates involved along the reaction pathway. On the basis of population analyses and comparison with prior calculations, the statistical picture is not suitable to describe the reactive atom-radical scattering processes, and the dynamics of the title reaction is believed to proceed through two competing dynamical pathways. The major low N″-components with significant vibrational excitation may be described by the direct abstraction process, while the minor but extraordinarily hot rotational distribution of high N″-components implies that some fraction of reactants is sampled to proceed through the indirect short-lived addition-complex forming process.

  5. Use of an Atmospheric Atomic Oxygen Beam for Restoration of Defaced Paintings

    Science.gov (United States)

    Banks, Bruce A.; Rutledge, Sharon K.; Karla, Margaret; Norris, Mary Jo; Real, William A.; Haytas, Christy A.

    1999-01-01

    An atmospheric atomic oxygen beam has been found to be effective in removing organic materials through oxidation that are typical of graffiti or other contaminant defacements which may occur to the surfaces of paintings. The technique, developed by the National Aeronautics and Space Administration, is portable and was successfully used at the Carnegie Museum of Art to remove a lipstick smudge from the surface of porous paint on the Andy Warhol painting "Bathtub." This process was also evaluated for suitability to remove felt tip and ball point ink graffiti from paper, gesso on canvas and cotton canvas.

  6. Atomic Oxygen Treatment as a Method of Recovering Smoke Damaged Paintings. Revised

    Science.gov (United States)

    Rutledge, Sharon K.; Banks, Bruce A.; Forkapa, Mark; Stueber, Thomas; Sechkar, Edward; Malinowski, Kevin

    1999-01-01

    A noncontact technique is described that uses atomic oxygen, generated under low pressure in the presence of nitrogen, to remove soot and charred varnish from the surface of a painting. The process, which involves surface oxidation, permits control of the amount of surface material removed. The effectiveness of the process was evaluated by reflectance measurements from selected areas made during the removal of soot from acrylic gesso, ink on paper, and varnished oil paint substrates. For the latter substrate, treatment also involved the removal of damaged varnish and paint binder from the surface.

  7. Efficiencies for production of atomic nitrogen and oxygen by relativistic proton impact in air

    Science.gov (United States)

    Porter, H. S.; Jackman, C. H.; Green, A. E. S.

    1976-01-01

    Relativistic electron and proton impact cross sections are obtained and represented by analytic forms which span the energy range from threshold to 1 GeV. For ionization processes, the Massey-Mohr continuum generalized oscillator strength surface is parameterized. Parameters are determined by simultaneous fitting to (1) empirical data, (2) the Bethe sum rule, and (3) doubly differential cross sections for ionization. Branching ratios for dissociation and predissociation from important states of N2 and O2 are determined. The efficiency for the production of atomic nitrogen and oxygen by protons with kinetic energy less than 1 GeV is determined using these branching ratio and cross section assignments.

  8. Barrier mechanism of multilayers graphene coated copper against atomic oxygen irradiation

    Science.gov (United States)

    Zhang, Haijing; Ren, Siming; Pu, Jibin; Xue, Qunji

    2018-06-01

    Graphene has been demonstrated as a protective coating for Cu under ambient condition because of its high impermeability and light-weight oxidation barrier. However, it lacks the research of graphene as a protective coating in space environment. Here, we experimentally and theoretically study the oxidation behavior of graphene-coated Cu in vacuum atomic oxygen (AO) condition. After AO irradiation, the experimental results show multilayer graphene has better anti-oxidation than monolayer graphene. Meanwhile, the calculation results show the oxidation appeared on the graphene's grain boundaries or the film's vacancy defects for the monolayer graphene coated Cu foil. Moreover, the calculation results show the oxidation process proceeds slowly in multilayers because of the matched defects overlaps each other to form a steric hindrance to suppress the O atom diffusion in the vertical direction, and the mismatched defects generates potential energy barriers for interlayer to suppress the O atom diffusion in the horizontal direction. Hence, multilayer graphene films could serve as protection coatings to prevent diffusion of O atom.

  9. Accelerated Oxygen Atom Transfer and C-H Bond Oxygenation by Remote Redox Changes in Fe3 Mn-Iodosobenzene Adducts.

    Science.gov (United States)

    de Ruiter, Graham; Carsch, Kurtis M; Gul, Sheraz; Chatterjee, Ruchira; Thompson, Niklas B; Takase, Michael K; Yano, Junko; Agapie, Theodor

    2017-04-18

    We report the synthesis, characterization, and reactivity of [LFe 3 (PhPz) 3 OMn( s PhIO)][OTf] x (3: x=2; 4: x=3), where 4 is one of very few examples of iodosobenzene-metal adducts characterized by X-ray crystallography. Access to these rare heterometallic clusters enabled differentiation of the metal centers involved in oxygen atom transfer (Mn) or redox modulation (Fe). Specifically, 57 Fe Mössbauer and X-ray absorption spectroscopy provided unique insights into how changes in oxidation state (Fe III 2 Fe II Mn II vs. Fe III 3 Mn II ) influence oxygen atom transfer in tetranuclear Fe 3 Mn clusters. In particular, a one-electron redox change at a distal metal site leads to a change in oxygen atom transfer reactivity by ca. two orders of magnitude. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Hydrogel brushes grafted from stainless steel via surface-initiated atom transfer radical polymerization for marine antifouling

    Science.gov (United States)

    Wang, Jingjing; Wei, Jun

    2016-09-01

    Crosslinked hydrogel brushes were grafted from stainless steel (SS) surfaces for marine antifouling. The brushes were prepared by surface-initiated atom transfer radical polymerization (SI-ATRP) of 2-methacryloyloxyethyl phosphorylcholine (MPC) and poly(ethylene glycol) methyl ether methacrylate (PEGMA) respectively with different fractions of crosslinker in the feed. The grafted layers prepared with different thickness were characterized by X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), ellipsometry and water contact angle measurements. With the increase in the fraction of crosslinker in the feed, the thickness of the grafted layer increased and the surface became smooth. All the brush-coated SS surfaces could effectively reduce the adhesion of bacteria and microalgae and settlement of barnacle cyprids, as compared to the pristine SS surface. The antifouling efficacy of the PEGMA polymer (PPEGMA)-grafted surface was higher than that of the MPC polymer (PMPC)-grafted surfaces. Furthermore, the crosslinked hydrogel brush-grafted surfaces exhibited better fouling resistance than the non-crosslinked polymer brush-grafted surfaces, and the antifouling efficacy increased with the crosslinking density. These hydrogel coatings of low toxicity and excellent anti-adhesive characteristics suggested their useful applications as environmentally friendly antifouling coatings.

  11. Hydrogel brushes grafted from stainless steel via surface-initiated atom transfer radical polymerization for marine antifouling

    International Nuclear Information System (INIS)

    Wang, Jingjing; Wei, Jun

    2016-01-01

    Highlights: • Crosslinked hydrogel brushes were grafted from SS surfaces for marine antifouling. • All brush-coated SS surfaces could effectively reduce the adhesion of biofouling. • The antifouling efficacy increased with the crosslinking density of hydrogels. - Abstract: Crosslinked hydrogel brushes were grafted from stainless steel (SS) surfaces for marine antifouling. The brushes were prepared by surface-initiated atom transfer radical polymerization (SI-ATRP) of 2-methacryloyloxyethyl phosphorylcholine (MPC) and poly(ethylene glycol) methyl ether methacrylate (PEGMA) respectively with different fractions of crosslinker in the feed. The grafted layers prepared with different thickness were characterized by X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), ellipsometry and water contact angle measurements. With the increase in the fraction of crosslinker in the feed, the thickness of the grafted layer increased and the surface became smooth. All the brush-coated SS surfaces could effectively reduce the adhesion of bacteria and microalgae and settlement of barnacle cyprids, as compared to the pristine SS surface. The antifouling efficacy of the PEGMA polymer (PPEGMA)-grafted surface was higher than that of the MPC polymer (PMPC)-grafted surfaces. Furthermore, the crosslinked hydrogel brush-grafted surfaces exhibited better fouling resistance than the non-crosslinked polymer brush-grafted surfaces, and the antifouling efficacy increased with the crosslinking density. These hydrogel coatings of low toxicity and excellent anti-adhesive characteristics suggested their useful applications as environmentally friendly antifouling coatings.

  12. Fabrication of ultrahydrophobic poly(lauryl acrylate) brushes on silicon wafer via surface-initiated atom transfer radical polymerization

    Energy Technology Data Exchange (ETDEWEB)

    Oztuerk, Esra; Turan, Eylem [Department of Chemistry, Faculty of Art and Science, Gazi University, 06500 Besevler, Ankara (Turkey); Caykara, Tuncer, E-mail: caykara@gazi.edu.tr [Department of Chemistry, Faculty of Art and Science, Gazi University, 06500 Besevler, Ankara (Turkey)

    2010-11-15

    In this report, ultrahydrophobic poly(lauryl acrylate) [poly(LA)] brushes were synthesized by surface-initiated atom transfer radical polymerization (SI-ATRP) of lauryl acrylate (LA) in N,N-dimethylformamide (DMF) at 90 deg. C. The formation of ultrahydrophobic poly(LA) films, whose thickness can be turned by changing polymerization time, is evidenced by using the combination of ellipsometry, X-ray photoelectron spectroscopy (XPS), grazing angle attenuated total reflectance-Fourier transform infrared spectroscopy (GATR-FTIR), atomic force microscopy (AFM), gel permeation chromatography (GPC), and water contact angle measurements. The SI-ATRP can be conducted in a well-controlled manner, as revealed by the linear kinetic plot, linear evolution of number-average molecular weights (M-bar{sub n}) versus monomer conversions, and the relatively narrow PDI (<1.28) of the grafted poly(LA) chains. The calculation of grafting parameters from experimental measurements indicated the synthesis of densely grafted poly(LA) films and allowed us to predict a 'brushlike' conformation for the chains in good solvent. The poly(LA) brushes exhibited high water contact angle of 163.3 {+-} 2.8{sup o}.

  13. Synthesis of thermoresponsive poly(N-isopropylacrylamide) brush on silicon wafer surface via atom transfer radical polymerization

    Energy Technology Data Exchange (ETDEWEB)

    Turan, Eylem; Demirci, Serkan [Department of Chemistry, Faculty of Art and Science, Gazi University, 06500 Besevler, Ankara (Turkey); Caykara, Tuncer, E-mail: caykara@gazi.edu.t [Department of Chemistry, Faculty of Art and Science, Gazi University, 06500 Besevler, Ankara (Turkey)

    2010-08-31

    Thermoresponsive poly(N-isopropylacrylamide) [poly(NIPAM)] brush on silicon wafer surface was prepared by combining the self-assembled monolayer of initiator and atom transfer radical polymerization (ATRP). The resulting polymer brush was characterized by in situ reflectance Fourier transform infrared spectroscopy, atomic force microscopy and ellipsometry techniques. Gel permeation chromatography determination of the number-average molecular weight and polydispersity index of the brush detached from the silicon wafer surface suggested that the surface-initiated ATRP method can provide relatively homogeneous polymer brush. Contact angle measurements exhibited a two-stage increase upon heating over the board temperature range 25-45 {sup o}C, which is in contrast to the fact that free poly(NIPAM) homopolymer in aqueous solution exhibits a phase transition at ca. 34 {sup o}C within a narrow temperature range. The first de-wetting transition takes place at 27 {sup o}C, which can be tentatively attributed to the n-cluster induced collapse of the inner region of poly(NIPAM) brush close to the silicon surface; the second de-wetting transition occurs at 38 {sup o}C, which can be attributed to the outer region of poly(NIPAM) brush, possessing much lower chain density compared to that of the inner part.

  14. Hydrogel brushes grafted from stainless steel via surface-initiated atom transfer radical polymerization for marine antifouling

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Jingjing, E-mail: jjwang1@hotmail.com; Wei, Jun

    2016-09-30

    Highlights: • Crosslinked hydrogel brushes were grafted from SS surfaces for marine antifouling. • All brush-coated SS surfaces could effectively reduce the adhesion of biofouling. • The antifouling efficacy increased with the crosslinking density of hydrogels. - Abstract: Crosslinked hydrogel brushes were grafted from stainless steel (SS) surfaces for marine antifouling. The brushes were prepared by surface-initiated atom transfer radical polymerization (SI-ATRP) of 2-methacryloyloxyethyl phosphorylcholine (MPC) and poly(ethylene glycol) methyl ether methacrylate (PEGMA) respectively with different fractions of crosslinker in the feed. The grafted layers prepared with different thickness were characterized by X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), ellipsometry and water contact angle measurements. With the increase in the fraction of crosslinker in the feed, the thickness of the grafted layer increased and the surface became smooth. All the brush-coated SS surfaces could effectively reduce the adhesion of bacteria and microalgae and settlement of barnacle cyprids, as compared to the pristine SS surface. The antifouling efficacy of the PEGMA polymer (PPEGMA)-grafted surface was higher than that of the MPC polymer (PMPC)-grafted surfaces. Furthermore, the crosslinked hydrogel brush-grafted surfaces exhibited better fouling resistance than the non-crosslinked polymer brush-grafted surfaces, and the antifouling efficacy increased with the crosslinking density. These hydrogel coatings of low toxicity and excellent anti-adhesive characteristics suggested their useful applications as environmentally friendly antifouling coatings.

  15. Determination of interstitial oxygen atom position in U2N3+xOy by near edge structure study

    Science.gov (United States)

    Jiang, A. K.; Zhao, Y. W.; Long, Z.; Hu, Y.; Wang, X. F.; Yang, R. L.; Bao, H. L.; Zeng, R. G.; Liu, K. Z.

    2018-06-01

    The determination of interstitial oxygen atom site in U2N3+xOy film could facilitate the understanding of the oxidation mechanism of α-U2N3 and the effect of U2N3+xOy on anti-oxidation. By comparing the similarities and variances between N K edge and O K edge electron energy loss spectra (EELS) for oxidized α-U2N3 and UO2, the present work looks at the local structure of nitrogen and oxygen atoms in U2N3+xOy film, identifying the most possible position of interstitial O atom.

  16. Effects of scavengers of reactive oxygen and radical species on cell survival following photodynamic treatment in vitro: comparison to ionizing radiation

    International Nuclear Information System (INIS)

    Henderson, B.W.; Miller, A.C.

    1986-01-01

    The effects of various scavengers of reactive oxygen and/or radical species on cell survival in vitro of EMT6 and CHO cells following photodynamic therapy (PDT) or gamma irradiation were compared. None of the agents used exhibited major direct cytotoxicity. Likewise, none interfered with cellular porphyrin uptake, and none except tryptophan altered singlet oxygen production during porphyrin illumination. The radioprotector cysteamine (MEA) was equally effective in reducing cell damage in both modalities. In part, this protection seems to have been induced by oxygen consumption in the system due to MEA autoxidation under formation of H 2 O 2 . The addition of catalase, which prevents H 2 O 2 buildup, reduced the effect of MEA to the same extent in both treatments. Whether the remaining protection was due to MEA's radical-reducing action or some remaining oxygen limitation is unclear. The protective action of MEA was not mediated by a doubling of cellular glutathione levels, since addition of buthionine sulfoximine, which prevented glutathione increase, did not diminish the observed MEA protection. The hydroxyl radical scavenger mannitol also afforded protection in both, but it was approximately twice as effective in gamma irradiation as in PDT. This is consistent with the predominant role of OH radicals in ionizing radiation damage and their presumed minor involvement in PDT damage. Superoxide dismutase, a scavenger of O 2 , acted as a radiation protector but was not significantly effective in PDT. Catalase, which scavenges H 2 O 2 , was ineffective in both modalities. Tryptophan, an efficient singlet oxygen scavenger, reduced cell death through PDT by several orders of magnitude while being totally ineffective in gamma irradiation. These data reaffirm the predominant role of 1O2 in the photodynamic cell killing but also indicate some involvement of free radical species

  17. A DFT Study of R-X Bond Dissociation Enthalpies of Relevance to the Initiation Process of Atom Transfer Radical Polymerization

    DEFF Research Database (Denmark)

    Gillies, Malcolm Bjørn; Matyjaszewski, Krzysztof; Norrby, Per-Ola

    2003-01-01

    DFT calculations at the B3P86/6-31G** level have been carried out to derive the bond dissociation energies (BDE) and free energies for a number of R-X systems (X ) Cl, Br, I, N3, and S2-CNMe2) that have been or can potentially be used as initiators for atom transfer radical polymerization (ATRP...

  18. Peptide block copolymers by N-carboxyanhydride ring-opening polymerization and atom transfer radical polymerization: The effect of amide macroinitiators

    NARCIS (Netherlands)

    Habraken, G.J.M.; Koning, C.E.; Heise, A.

    2009-01-01

    The synthesis of polypeptide-containing block copolymers combining N-carboxyanhydride (NCA) ring-opening polymerization and atom transfer radical polymerization (ATRP) was investigated. An amide initiator comprising an amine function for the NCA polymerization and an activated bromide for ATRP was

  19. Synthesis of poly(2-ethyl-2-oxazoline)-b-poly(styrene) copolymers via a dual initiator route combining cationic ring-opening polymerization and atom transfer radical polymerization

    NARCIS (Netherlands)

    Becer, C.R.; Paulus, R.M.; ppener, S.; Hoogenboom, R.; Fustin, C.A.; Gohy, J.M.W.; Schubert, U.S.

    2008-01-01

    Block copolymers of 2-ethyl-2-oxazoline (EtOx) and styrene were synthesized by a combination of cationic ring-opening polymerization (CROP) and atom transfer radical polymerization (ATRP). Initially, a detailed kinetic investigation for the ?-bromoisobutyrylbromide (BrEBBr) initiated CROP of EtOx

  20. Acrylamide-b-N-isopropylacrylamide block copolymers : Synthesis by atomic transfer radical polymerization in water and the effect of the hydrophilic-hydrophobic ratio on the solution properties

    NARCIS (Netherlands)

    Wever, Diego Armando Z.; Ramalho, Graham; Picchioni, Francesco; Broekhuis, Antonius Augustinus

    2014-01-01

    A series of block copolymers of acrylamide and N-isopropylacrylamide (NIPAM) characterized by different ratios between the length of the two blocks have been prepared through atomic transfer radical polymerization in water at room temperature. The solution properties of the block copolymers were

  1. Oxygen radicals in experimental shock: effects of spin-trapping nitrones in ameliorating shock pathophysiology (see comments)

    Energy Technology Data Exchange (ETDEWEB)

    Novelli, G.P. (Institute of Anesthesiology and Intensive Care, University of Florence, Careggi Hospital, (Italy))

    1992-04-01

    Circulatory shock is accepted as a consequence of an acute oxygen radical overgeneration. Spin-trapping nitrones inactivate free radicals by forming relatively stable adducts. Three spin-trapping nitrones (N-tert-phenyl-butyl-nitrone; alpha-4-pyridyl-oxide-N-tert-butyl-nitrone; 5-5,dimethyl,1,pyrroline-N-oxide) were tested regarding their role in the pathophysiology and evolution of circulatory shock in rats. A prospective, randomized, controlled trial of spin-trapping nitrones in rats experiencing three different models of circulatory shock was designed. In the first group, endotoxic, traumatic, and mesenteric artery occlusion shock (all 100% lethal in control experiments) was prevented by the ip administration of N-tert-phenyl-butyl-nitrone (150 mg/kg); alpha-4-pyridyl-oxide-N-tert-butyl-nitrone (100 mg/kg); or 5-5,dimethyl,1,pyrroline-N-oxide (100 mg/kg). However, the evolution of shock was unaffected by the same compounds when all three nitrones had been previously inactivated by exposure to light and air. In the second group, microcirculatory derangements that were provoked by endotoxin and were observed in the mesocecum of rats were completely prevented by pretreatment with either peritoneal administration of each of the three nitrones or by their topical application to the microscopic field. While the rats survived after systemic treatment, those rats receiving topical nitrones died from endotoxic shock. In the third group, cell-membrane stiffness (a sign of peroxidative damage) was measured by spin-probes and electron-spin resonance in mitochondrial and microsomal membranes. Cell membranes obtained from shocked rats were more rigid than those membranes of controls. However, the membranes obtained from rats that were submitted to trauma or endotoxin after pretreatment with N-tert-phenyl-butyl-nitrone had normal stiffness.

  2. MISSE 2 PEACE Polymers Experiment Atomic Oxygen Erosion Yield Error Analysis

    Science.gov (United States)

    McCarthy, Catherine E.; Banks, Bruce A.; deGroh, Kim, K.

    2010-01-01

    Atomic oxygen erosion of polymers in low Earth orbit (LEO) poses a serious threat to spacecraft performance and durability. To address this, 40 different polymer samples and a sample of pyrolytic graphite, collectively called the PEACE (Polymer Erosion and Contamination Experiment) Polymers, were exposed to the LEO space environment on the exterior of the International Space Station (ISS) for nearly 4 years as part of the Materials International Space Station Experiment 1 & 2 (MISSE 1 & 2). The purpose of the PEACE Polymers experiment was to obtain accurate mass loss measurements in space to combine with ground measurements in order to accurately calculate the atomic oxygen erosion yields of a wide variety of polymeric materials exposed to the LEO space environment for a long period of time. Error calculations were performed in order to determine the accuracy of the mass measurements and therefore of the erosion yield values. The standard deviation, or error, of each factor was incorporated into the fractional uncertainty of the erosion yield for each of three different situations, depending on the post-flight weighing procedure. The resulting error calculations showed the erosion yield values to be very accurate, with an average error of 3.30 percent.

  3. Toward a New Capability for Upper Atmospheric Research using Atomic Oxygen Lidar

    Science.gov (United States)

    Clemmons, J. H.; Steinvurzel, P.; Mu, X.; Beck, S. M.; Lotshaw, W. T.; Rose, T. S.; Hecht, J. H.; Westberg, K. R.; Larsen, M. F.; Chu, X.; Fritts, D. C.

    2017-12-01

    Progress on development of a lidar system for probing the upper atmosphere based on atomic oxygen resonance is presented and discussed. The promise of a fully-developed atomic oxygen lidar system, which must be based in space to measure the upper atmosphere, for yielding comprehensive new insights is discussed in terms of its potential to deliver global, height-resolved measurements of winds, temperature, and density at a high cadence. An overview of the system is given, and its measurement principles are described, including its use of 1) a two-photon transition to keep the optical depth low; 2) laser tuning to provide the Doppler information needed to measure winds; and 3) laser tuning to provide a Boltzmann temperature measurement. The current development status is presented with a focus on what has been done to demonstrate capability in the laboratory and its evolution to a funded sounding rocket investigation designed to make measurements of three-dimensional turbulence in the upper mesosphere and lower thermosphere.

  4. Leveling coatings for reducing the atomic oxygen defect density in protected graphite fiber epoxy composites

    Science.gov (United States)

    Jaworske, D. A.; Degroh, Kim K.; Podojil, G.; McCollum, T.; Anzic, J.

    1992-11-01

    Pinholes or other defect sites in a protective oxide coating provide pathways for atomic oxygen in low Earth orbit to reach underlying material. One concept of enhancing the lifetime of materials in low Earth orbit is to apply a leveling coating to the material prior to applying any reflective and protective coatings. Using a surface tension leveling coating concept, a low viscosity epoxy was applied to the surface of several composite coupons. A protective layer of 1000 A of SiO2 was deposited on top of the leveling coating, and the coupons were exposed to an atomic oxygen environment in a plasma asher. Pinhole populations per unit area were estimated by counting the number of undercut sites observed by scanning electron microscopy. Defect density values of 180,000 defects/sq cm were reduced to about 1000 defects/sq cm as a result of the applied leveling coating. These improvements occur at a mass penalty of about 2.5 mg/sq cm.

  5. Reactive oxygen radicals and gaseous transmitters in carotid body activation by intermittent hypoxia.

    Science.gov (United States)

    Prabhakar, Nanduri R; Peng, Ying-Jie; Yuan, Guoxiang; Nanduri, Jayasri

    2018-05-01

    Sleep apnea is a prevalent respiratory disease characterized by periodic cessation of breathing during sleep causing intermittent hypoxia (IH). Sleep apnea patients and rodents exposed to IH exhibit elevated sympathetic nerve activity and hypertension. A heightened carotid body (CB) chemoreflex has been implicated in causing autonomic abnormalities in IH-treated rodents and in sleep apnea patients. The purpose of this article is to review the emerging evidence showing that interactions between reactive oxygen species (ROS) and gaseous transmitters as a mechanism cause hyperactive CB by IH. Rodents treated with IH exhibit markedly elevated ROS in the CB, which is due to transcriptional upregulation of pro-oxidant enzymes by hypoxia-inducible factor (HIF)-1 and insufficient transcriptional regulation of anti-oxidant enzymes by HIF-2. ROS, in turn, increases cystathionine γ-lyase (CSE)-dependent H 2 S production in the CB. Blockade of H 2 S synthesis prevents IH-evoked CB activation. However, the effects of ROS on H 2 S production are not due to direct effects on CSE enzyme activity but rather due to inactivation of heme oxygenase-2 (HO-2), a carbon monoxide (CO) producing enzyme. CO inhibits H 2 S production through inactivation of CSE by PKG-dependent phosphorylation. During IH, reduced CO production resulting from inactivation of HO-2 by ROS releases the inhibition of CO on CSE thereby increasing H 2 S. Inhibiting H 2 S synthesis prevented IH-evoked sympathetic activation and hypertension.

  6. Biphasic effect of oxygen radicals on prostaglandin production by rat mesangial cells

    International Nuclear Information System (INIS)

    Adler, S.; Stahl, R.A.K.; Baker, P.J.; Chen, Y.P.; Pritzl, P.M.; Couser, W.G.

    1987-01-01

    Cultured rat mesangial cells were exposed to a reactive oxygen species (ROS) generating system (xanthine plus xanthine oxidase) to explore the effect of ROS on their metabolism of arachidonic acid (AA). Cell viability, as assessed by 51 Cr release, was not affected by the concentrations of xanthine plus xanthine oxidase used. Prostaglandin E 2 (PGE 2 ) production following exposure to increasing quantities of xanthine plus xanthine oxidase was significantly decreased when cells were stimulated with the calcium ionophore A23187 or AA. Maximum suppression of production was seen within 10 min of ROS exposure. Thromboxane B 2 production was similarly decreased. This effect was reversed by addition of catalase to the ROS generating system but not by superoxide dismutase or mannitol, which suggested that H 2 O 2 was the responsible metabolite. High levels of H 2 O 2 suppressed PGE 2 production. Lower levels of H 2 O 2 resulted in significant stimulation of base-line PGE 2 production. Analysis of release of 3 H]AA-labeled metabolites from A23187-stimulated cells showed no effect of H 2 O 2 on phospholipase activity. Thus ROS can stimulate or inhibitor AA metabolism in the glomerular mesangium, which may have important effects on glomerular hemodynamics during glomerular injury

  7. Does ibuprofen treatment in patent ductus arteriosus alter oxygen free radicals in premature infants?

    Science.gov (United States)

    Akar, Melek; Yildirim, Tulin G; Sandal, Gonca; Bozdag, Senol; Erdeve, Omer; Altug, Nahide; Uras, Nurdan; Oguz, Serife S; Dilmen, Ugur

    2017-04-01

    Introduction Ibuprofen is used widely to close patent ductus arteriosus in preterm infants. The anti-inflammatory activity of ibuprofen may also be partly due to its ability to scavenge reactive oxygen species and reactive nitrogen species. We evaluated the interaction between oxidative status and the medical treatment of patent ductus arteriosus with two forms of ibuprofen. Materials and methods This study enrolled newborns of gestational age ⩽32 weeks, birth weight ⩽1500 g, and postnatal age 48-96 hours, who received either intravenous or oral ibuprofen to treat patent ductus arteriosus. Venous blood was sampled before ibuprofen treatment from each patient to determine antioxidant and oxidant concentrations. Secondary samples were collected 24 hours after the end of the treatment. Total oxidant status and total antioxidant capacity were measured using Erel's method. This prospective randomised study enrolled 102 preterm infants with patent ductus arteriosus. The patent ductus arteriosus closure rate was significantly higher in the oral ibuprofen group (84.6 versus 62%) after the first course of treatment (p=0.011). No significant difference was found between the pre- and post-treatment total oxidant status and total antioxidant capacity in the groups. Discussion Ibuprofen treatment does not change the total oxidant status or total antioxidant capacity. We believe that the effect of ibuprofen treatment in inducing ischaemia overcomes the scavenging effect of ibuprofen.

  8. On I(5577 Å and I (7620 Å auroral emissions and atomic oxygen densities

    Directory of Open Access Journals (Sweden)

    R. L. Gattinger

    Full Text Available A model of auroral electron deposition processes has been developed using Monte Carlo techniques to simulate electron transport and energy loss. The computed differential electron flux and pitch angle were compared with in situ auroral observations to provide a check on the accuracy of the model. As part of the energy loss process, a tally was kept of electronic excitation and ionization of the important atomic and molecular states. The optical emission rates from these excited states were computed and compared with auroral observations of η(3914 Å, η(5577 Å, η(7620 Å and η(N2VK. In particular, the roles played by energy transfer from N2(A3Σ+u and by other processes in the excitation of O(1S and O2(b1Σ+g were investigated in detail. It is concluded that the N2(A3Σ+u mechanism is dominant for the production of OI(5577 Å in the peak emission region of normal aurora, although the production efficiency is much smaller than the measured laboratory value; above 150 km electron impact on atomic oxygen is dominant. Atomic oxygen densities in the range of 0.75±0.25 MSIS-86 [O] were derived from the optical comparisons for auroral latitudes in mid-winter for various levels of solar and magnetic activity.

  9. Critical role of oxygen radicals in the initiation of hepatic depression after trauma hemorrhage.

    Science.gov (United States)

    Jarrar, D; Wang, P; Cioffi, W G; Bland, K I; Chaudry, I H

    2000-11-01

    Although depression in hepatocellular function occurs early after trauma and severe hemorrhage and persists despite fluid resuscitation, it remains unknown whether reactive oxygen species (ROS) play any role in the initiation of hepatocellular depression and damage under those conditions. We hypothesized that administration of a ROS scavenger at the beginning of resuscitation will attenuate organ injury after severe shock. Male Sprague-Dawley rats (275-325 g) underwent laparotomy (i.e., induction of soft tissue trauma) and were then bled to and maintained at a mean arterial pressure of 40 mm Hg until 40% of the maximal bleed-out volume was returned in the form of Ringer's lactate. The animals were then resuscitated with four times the volume of maximal bleed-out with RL over 60 minutes. The ROS scavenger 2-mercaptopropionyl glycine (30 mg/kg) or vehicle was administered intravenously as a bolus at the beginning of resuscitation. At 2 hours after the completion of crystalloid resuscitation or the equivalent interval after sham-operation, cardiac index was measured by a dye dilution technique. Hepatocellular function, i.e., the maximum velocity of indocyanine green clearance (Vmax) and the efficiency of the active transport (Km), was determined using an in vivo hemoreflectometer. Serum levels of tumor necrosis factor (TNF)-alpha and alanine aminotransferase were determined with ELISA and colorimetrically, respectively. The results indicate that at 2 hours after trauma hemorrhage and resuscitation, cardiac index and hepatocellular function were markedly depressed with concomitantly increased serum levels of TNF-alpha and alanine aminotransferase (p hepatic function and markedly attenuated liver enzyme release and serum levels of TNF-alpha (p trauma hemorrhage and resuscitation.

  10. Stability of V2O5 Supported on Titania in the Presence of Water, Bulk Oxygen Vacancies, and Adsorbed Oxygen Atoms

    DEFF Research Database (Denmark)

    Kristoffersen, Henrik Høgh; Neilson, Hunter L.; Buratto, Steven K.

    2017-01-01

    ). In the case of oxidative dehydrogenation of alkanes and methanol, the reaction produces water, oxygen vacancies, and hydrogen atoms bound to the surface. For this article we use density functional theory to examine how the presence of these species on the surface affects a V2O5 cluster, which we assume......A catalyst consisting of vanadium oxide submonolayers supported on rutile titanium dioxide is used for a variety of reactions. One important question is the difference between the activity of monomeric clusters (having one vanadium atom) and polymeric clusters (having more than one vanadium atom...

  11. Excitation and charge transfer in low-energy hydrogen atom collisions with neutral oxygen

    Science.gov (United States)

    Barklem, P. S.

    2018-02-01

    Excitation and charge transfer in low-energy O+H collisions is studied; it is a problem of importance for modelling stellar spectra and obtaining accurate oxygen abundances in late-type stars including the Sun. The collisions have been studied theoretically using a previously presented method based on an asymptotic two-electron linear combination of atomic orbitals (LCAO) model of ionic-covalent interactions in the neutral atom-hydrogen-atom system, together with the multichannel Landau-Zener model. The method has been extended to include configurations involving excited states of hydrogen using an estimate for the two-electron transition coupling, but this extension was found to not lead to any remarkably high rates. Rate coefficients are calculated for temperatures in the range 1000-20 000 K, and charge transfer and (de)excitation processes involving the first excited S-states, 4s.5So and 4s.3So, are found to have the highest rates. Data are available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (http://130.79.128.5) or via http://cdsarc.u-strasbg.fr/vizbin/qcat?J/A+A/610/A57. The data are also available at http://https://github.com/barklem/public-data

  12. [Generation of Superoxide Radicals by Complex III in Heart Mitochondria and Antioxidant Effect of Dinitrosyl Iron Complexes at Different Partial Pressure of Oxygen].

    Science.gov (United States)

    Dudylina, A L; Ivanova, M V; Shumaev, K B; Ruuge, E K

    2016-01-01

    The EPR spin-trapping technique and EPR-oximetry were used to study generation of superoxide radicals in heart mitochondria isolated from Wistar rats under conditions of variable oxygen concentration. Lithium phthalocyanine and TEMPONE-15N-D16 were chosen to determine oxygen content in a gas-permeable capillary tube containing mitochondria. TIRON was used as a spin trap. We investigated the influence of different oxygen concentrations in incubation mixture and demonstrated that heart mitochondria can generate superoxide in complex III at different partial pressure of oxygen as well as under the conditions of deep hypoxia (partial pressure of oxygen, but the magnitude and kinetic characteristics of the effect depended on the concentration of the drug.

  13. Oxoferryl-Porphyrin Radical Catalytic Intermediate in Cytochrome bd Oxidases Protects Cells from Formation of Reactive Oxygen Species*

    Science.gov (United States)

    Paulus, Angela; Rossius, Sebastiaan Gijsbertus Hendrik; Dijk, Madelon; de Vries, Simon

    2012-01-01

    The quinol-linked cytochrome bd oxidases are terminal oxidases in respiration. These oxidases harbor a low spin heme b558 that donates electrons to a binuclear heme b595/heme d center. The reaction with O2 and subsequent catalytic steps of the Escherichia coli cytochrome bd-I oxidase were investigated by means of ultra-fast freeze-quench trapping followed by EPR and UV-visible spectroscopy. After the initial binding of O2, the O–O bond is heterolytically cleaved to yield a kinetically competent heme d oxoferryl porphyrin π-cation radical intermediate (compound I) magnetically interacting with heme b595. Compound I accumulates to 0.75–0.85 per enzyme in agreement with its much higher rate of formation (∼20,000 s−1) compared with its rate of decay (∼1,900 s−1). Compound I is next converted to a short lived heme d oxoferryl intermediate (compound II) in a phase kinetically matched to the oxidation of heme b558 before completion of the reaction. The results indicate that cytochrome bd oxidases like the heme-copper oxidases break the O–O bond in a single four-electron transfer without a peroxide intermediate. However, in cytochrome bd oxidases, the fourth electron is donated by the porphyrin moiety rather than by a nearby amino acid. The production of reactive oxygen species by the cytochrome bd oxidase was below the detection level of 1 per 1000 turnovers. We propose that the two classes of terminal oxidases have mechanistically converged to enzymes in which the O–O bond is broken in a single four-electron transfer reaction to safeguard the cell from the formation of reactive oxygen species. PMID:22287551

  14. Pancreatic nitric oxide and oxygen free radicals in the early stages of streptozotocin-induced diabetes mellitus in the rat

    Directory of Open Access Journals (Sweden)

    González E.

    2000-01-01

    Full Text Available The objective of the present study was to explore the regulatory mechanisms of free radicals during streptozotocin (STZ-induced pancreatic damage, which may involve nitric oxide (NO production as a modulator of cellular oxidative stress. Removal of oxygen species by incubating pancreatic tissues in the presence of polyethylene glycol-conjugated superoxide dismutase (PEG-SOD (1 U/ml produced a decrease in nitrite levels (42% and NO synthase (NOS activity (50% in diabetic but not in control samples. When NO production was blocked by N G-monomethyl-L-arginine (L-NMMA (600 µM, SOD activity increased (15.21 ± 1.23 vs 24.40 ± 2.01 U/mg dry weight. The increase was abolished when the NO donor, spermine nonoate, was added to the incubating medium (13.2 ± 1.32. Lipid peroxidation was lower in diabetic tissues when PEG-SOD was added (0.40 ± 0.02 vs 0.20 ± 0.03 nmol/mg protein, and when L-NMMA blocked NOS activity in the incubating medium (0.28 ± 0.05; spermine nonoate (100 µM abolished the decrease in lipoperoxide level (0.70 ± 0.02. We conclude that removal of oxygen species produces a decrease in pancreatic NO and NOS levels in STZ-treated rats. Moreover, inhibition of NOS activity produces an increase in SOD activity and a decrease in lipoperoxidation in diabetic pancreatic tissues. Oxidative stress and NO pathway are related and seem to modulate each other in acute STZ-induced diabetic pancreas in the rat.

  15. Two-photon absorption laser-induced fluorescence of atomic oxygen in the afterglow of pulsed positive corona discharge

    Science.gov (United States)

    Ono, Ryo; Takezawa, Kei; Oda, Tetsuji

    2009-08-01

    Atomic oxygen is measured in the afterglow of pulsed positive corona discharge using time-resolved two-photon absorption laser-induced fluorescence. The discharge occurs in a 14 mm point-to-plane gap in dry air. After the discharge pulse, the atomic oxygen density decreases at a rate of 5×104 s-1. Simultaneously, ozone density increases at almost the same rate, where the ozone density is measured using laser absorption method. This agreement between the increasing rate of atomic oxygen and decreasing rate of ozone proves that ozone is mainly produced by the well-known three-body reaction, O+O2+M→O3+M. No other process for ozone production such as O2(v)+O2→O3+O is observed. The spatial distribution of atomic oxygen density is in agreement with that of the secondary streamer luminous intensity. This agreement indicates that atomic oxygen is mainly produced in the secondary streamer channels, not in the primary streamer channels.

  16. Atomic oxygen effects on boron nitride and silicon nitride: A comparison of ground based and space flight data

    Science.gov (United States)

    Cross, J. B.; Lan, E. H.; Smith, C. A.; Whatley, W. J.

    1990-01-01

    The effects of atomic oxygen on boron nitride (BN) and silicon nitride (Si3N4) were evaluated in a low Earth orbit (LEO) flight experiment and in a ground based simulation facility. In both the inflight and ground based experiments, these materials were coated on thin (approx. 250A) silver films, and the electrical resistance of the silver was measured in situ to detect any penetration of atomic oxygen through the BN and Si3N4 materials. In the presence of atomic oxygen, silver oxidizes to form silver oxide, which has a much higher electrical resistance than pure silver. Permeation of atomic oxygen through BN, as indicated by an increase in the electrical resistance of the silver underneath, was observed in both the inflight and ground based experiments. In contrast, no permeation of atomic oxygen through Si3N4 was observed in either the inflight or ground based experiments. The ground based results show good qualitative correlation with the LEO flight results, indicating that ground based facilities such as the one at Los Alamos National Lab can reproduce space flight data from LEO.

  17. Mechanisms of electron transfer from structrual Fe(II) in reduced nontronite to oxygen for production of hydroxyl radicals

    Science.gov (United States)

    Yuan, Songhu; Liu, Xixiang; Liao, Wenjuan; Zhang, Peng; Wang, Xiaoming; Tong, Man

    2018-02-01

    Production of hydroxyl radicals (radOH) has been recently revealed upon oxygenation of sediments in redox-dynamic subsurface environments. In particular, Fe(II)-bearing clay minerals are the major sediment components contributing to radOH production upon oxygenation, and the produced radOH can oxidize contaminants and inactivate bacteria. Whereas, the mechanisms of radOH production from oxygenation of Fe(II)-bearing clay minerals remain elusive. The objectives of this study were to identify the structural variation of Fe(II) entities during the oxidation of Fe(II)-bearing clay minerals by O2, and to unravel the mechanisms of electron transfer within the mineral structure and from mineral to O2 for radOH production. Nontronite (NAu-2, 23% Fe) which was chemically reduced to 54.5% Fe(II) in total Fe was used as a model Fe(II)-bearing clay mineral. Production of radOH and oxidation of Fe(II) were measured during the oxidation of reduced NAu-2 by O2. A wide spectrum of spectroscopic techniques, including Fourier transform infrared spectroscopy (FTIR), Fe K-edge X-ray absorption spectroscopy (XAS), Mössbauer spectra, and X-ray photoelectron spectroscopy (XPS), were employed to explore the structural variation of Fe(II) entities in NAu-2 and the electron transfer within NAu-2 and from NAu-2 to O2. For 180 min oxidation of 1 g/L reduced NAu-2, a biphasic radOH production was observed, being quick within the initial 15 min and slow afterwards. Production of radOH correlates well with oxidation of Fe(II) in the reduced NAu-2. Within the initial 15 min, trioctahedral Fe(II)-Fe(II)-Fe(II) entities and edge Fe(II) in the reduced NAu-2 were preferentially and quickly oxidized, and electrons from the interior Fe(II)-Fe(II)-Fe(II) entities were most likely ejected from the basal siloxane plane to O2. Meanwhile, trioctahedral Fe(II)-Fe(II)-Fe(II) entities were mainly transformed to dioctahedral Fe(II)-Fe(II) entities. When the time of oxygenation was longer than 15 min

  18. Manganese-Oxygen Intermediates in O-O Bond Activation and Hydrogen-Atom Transfer Reactions.

    Science.gov (United States)

    Rice, Derek B; Massie, Allyssa A; Jackson, Timothy A

    2017-11-21

    Biological systems capitalize on the redox versatility of manganese to perform reactions involving dioxygen and its derivatives superoxide, hydrogen peroxide, and water. The reactions of manganese enzymes influence both human health and the global energy cycle. Important examples include the detoxification of reactive oxygen species by manganese superoxide dismutase, biosynthesis by manganese ribonucleotide reductase and manganese lipoxygenase, and water splitting by the oxygen-evolving complex of photosystem II. Although these enzymes perform very different reactions and employ structurally distinct active sites, manganese intermediates with peroxo, hydroxo, and oxo ligation are commonly proposed in catalytic mechanisms. These intermediates are also postulated in mechanisms of synthetic manganese oxidation catalysts, which are of interest due to the earth abundance of manganese. In this Account, we describe our recent efforts toward understanding O-O bond activation pathways of Mn III -peroxo adducts and hydrogen-atom transfer reactivity of Mn IV -oxo and Mn III -hydroxo complexes. In biological and synthetic catalysts, peroxomanganese intermediates are commonly proposed to decay by either Mn-O or O-O cleavage pathways, although it is often unclear how the local coordination environment influences the decay mechanism. To address this matter, we generated a variety of Mn III -peroxo adducts with varied ligand environments. Using parallel-mode EPR and Mn K-edge X-ray absorption techniques, the decay pathway of one Mn III -peroxo complex bearing a bulky macrocylic ligand was investigated. Unlike many Mn III -peroxo model complexes that decay to oxo-bridged-Mn III Mn IV dimers, decay of this Mn III -peroxo adduct yielded mononuclear Mn III -hydroxo and Mn IV -oxo products, potentially resulting from O-O bond activation of the Mn III -peroxo unit. These results highlight the role of ligand sterics in promoting the formation of mononuclear products and mark an important

  19. Influence of average ion energy and atomic oxygen flux per Si atom on the formation of silicon oxide permeation barrier coatings on PET

    Science.gov (United States)

    Mitschker, F.; Wißing, J.; Hoppe, Ch; de los Arcos, T.; Grundmeier, G.; Awakowicz, P.

    2018-04-01

    The respective effect of average incorporated ion energy and impinging atomic oxygen flux on the deposition of silicon oxide (SiO x ) barrier coatings for polymers is studied in a microwave driven low pressure discharge with additional variable RF bias. Under consideration of plasma parameters, bias voltage, film density, chemical composition and particle fluxes, both are determined relative to the effective flux of Si atoms contributing to film growth. Subsequently, a correlation with barrier performance and chemical structure is achieved by measuring the oxygen transmission rate (OTR) and by performing x-ray photoelectron spectroscopy. It is observed that an increase in incorporated energy to 160 eV per deposited Si atom result in an enhanced cross-linking of the SiO x network and, therefore, an improved barrier performance by almost two orders of magnitude. Furthermore, independently increasing the number of oxygen atoms to 10 500 per deposited Si atom also lead to a comparable barrier improvement by an enhanced cross-linking.

  20. Atmospheric plasma generates oxygen atoms as oxidizing species in aqueous solutions

    International Nuclear Information System (INIS)

    Hefny, Mohamed Mokhtar; Pattyn, Cedric; Benedikt, Jan; Lukes, Petr

    2016-01-01

    A remote microscale atmospheric pressure plasma jet ( µ APPJ) with He, He/H 2 O, He/O 2 , and He/O 2 /H 2 O gas mixtures was used to study the transport of reactive species from the gas phase into the liquid and the following aqueous phase chemistry. The effects induced by the µ APPJ in water were quantitatively studied using phenol as a chemical probe and by measuring H 2 O 2 concentration and pH values. These results were combined with the analysis of the absolute densities of the reactive species and the modeling of convective/diffusion transport and recombination reactions in the effluent of the plasma jet. Additionally, modified plasma jets were used to show that the role of emitted photons in aqueous chemistry is negligible for these plasma sources. The fastest phenol degradation was measured for the He/O 2 plasma, followed by He/H 2 O, He/O 2 /H 2 O, and He plasmas. The modeled quantitative flux of O atoms into the liquid in the He/O 2 plasma case was highly comparable with the phenol degradation rate and showed a very high transfer efficiency of reactive species from the plasma into the liquid, where more than half of the O atoms leaving the jet nozzle entered the liquid. The results indicate that the high oxidative effect of He/O 2 plasma was primarily due to solvated O atoms, whereas OH radicals dominated the oxidative effects induced in water by plasmas with other gas mixtures. These findings help to understand, in a quantitative way, the complex interaction of cold atmospheric plasmas with aqueous solutions and will allow a better understanding of the interaction of these plasmas with water or buffered solutions containing biological macromolecules, microorganisms, or even eukaryotic cells. Additionally, the µ APPJ He/O 2 plasma source seems to be an ideal tool for the generation of O atoms in aqueous solutions for any future studies of their reactivity. (paper)

  1. Rational preparation of dibenzothiophene-imprinted polymers by surface imprinting technique combined with atom transfer radical polymerization

    International Nuclear Information System (INIS)

    Yang, Wenming; Liu, Lukuan; Zhou, Zhiping; Liu, Hong; Xie, Binze; Xu, Wanzhen

    2013-01-01

    A computational simulation method is introduced to simulate the dibenzothiophene-monomer pre-assembly system of molecular imprinted polymers. The interaction type and intensity between dibenzothiophene and monomer are discussed from the binding energy and spatial position distribution. The simulation and analysis results indicate that the amount of the function monomer is not the more the better in preparing molecular imprinted polymers. Based on the above results, a novel dibenzothiophene-imprinted polymers with the favorable specific adsorption effect was prepared by surface imprinting technique combined with atom transfer radical polymerization. This combined technologies are used for preparing a desulfurization adsorbent for the first time. Various measures were selected to characterize the structure and morphology of the prepared adsorbent. The characterization results show that the adsorbent has suitable features for further adsorption process. A series of static adsorption experiments were conducted to analyze its adsorption performance. The adsorption process follows Elovich model by the kinetic analysis and Sips equation by the isothermal analysis. The approach we described will provide another opportunity in the deep desulfurization field.

  2. Antifouling coatings via plasma polymerization and atom transfer radical polymerization on thin film composite membranes for reverse osmosis

    Science.gov (United States)

    Hirsch, Ulrike; Ruehl, Marco; Teuscher, Nico; Heilmann, Andreas

    2018-04-01

    A major drawback to otherwise highly efficient membrane-based desalination techniques like reverse osmosis (RO) is the susceptibility of the membranes to biofouling. In this work, a combination of plasma activation, plasma bromination and surface-initiated atom transfer radical polymerization (si-ATRP) of hydrophilic and zwitterionic monomers, namely hydroxyethyl methacrylate (HEMA), 2-methacryloyloxyethyl phosphorylcholine (MPC) and [2-(methacryloyloxy)ethyl]-dimethyl-(3-sulfopropyl)ammonium hydroxide (SBMA), was applied to generate non-specific, anti-adhesive coatings on thin film composite (TFC) membranes. The antifouling effect of the coatings was shown by short-time batch as well as long-time steady state cultivation experiments with the microorganism Pseudomonas fluorescens. It could be shown that plasma functionalization and polymerization is possible on delicate thin film composite membranes without restricting their filtration performance. All modified membranes showed an increased resistance towards the adhesion of Pseudomonas fluorescens. On average, the biofilm coverage was reduced by 51.4-12.6% (for HEMA, SBMA, and MPC), the highest reduction was monitored for MPC with a biofilm reduction by 85.4%. The hydrophilic coatings applied did not only suppress the adhesion of Pseudomonas fluorescens, but also significantly increase the permeate flux of the membranes relative to uncoated membranes. The stability of the coatings was however not ideal and will have to be improved for future commercial use.

  3. All solid-state polymer electrolytes prepared from a hyper-branched graft polymer using atom transfer radical polymerization

    International Nuclear Information System (INIS)

    Higa, Mitsuru; Fujino, Yukiko; Koumoto, Taihei; Kitani, Ryousuke; Egashira, Satsuki

    2005-01-01

    We propose an all solid-state (liquid free) polymer electrolyte (SPE) prepared from a hyper-branched graft copolymer. The graft copolymer consisting of a poly(methyl methacrylate) main chain and poly(ethylene glycol) methyl ether methacrylate side chains was synthesized by atom transfer radical polymerization changing the average chain distance between side chains, side chain length and branched chain length of the proposed structure of the graft copolymer. The ionic conductivity of the SPEs increases with increasing the side chain length, branched chain length and/or average distance between the side chains. The ionic conductivity of the SPE prepared from POEM 9 whose POEM content = 51 wt% shows 2 x 10 -5 S/cm at 30 deg. C. The tensile strength of the SPEs decreases with increases the side chain length, branched chain length and/or average distance between the side chains. These results indicate that a SPE prepared from the hyper-branched graft copolymer has potential to be applied to an all-solid polymer electrolyte

  4. In Situ Investigation of Electrochemically Mediated Surface-Initiated Atom Transfer Radical Polymerization by Electrochemical Surface Plasmon Resonance.

    Science.gov (United States)

    Chen, Daqun; Hu, Weihua

    2017-04-18

    Electrochemically mediated atom transfer radical polymerization (eATRP) initiates/controls the controlled/living ATRP chain propagation process by electrochemically generating (regenerating) the activator (lower-oxidation-state metal complex) from deactivator (higher-oxidation-state metal complex). Despite successful demonstrations in both of the homogeneous polymerization and heterogeneous systems (namely, surface-initiated ATRP, SI-ATRP), the eATRP process itself has never been in situ investigated, and important information regarding this process remains unrevealed. In this work, we report the first investigation of the electrochemically mediated SI-ATRP (eSI-ATRP) by rationally combining the electrochemical technique with real-time surface plasmon resonance (SPR). In the experiment, the potential of a SPR gold chip modified by the self-assembled monolayer of the ATRP initiator was controlled to electrochemically reduce the deactivator to activator to initiate the SI-ATRP, and the whole process was simultaneously monitored by SPR with a high time resolution of 0.1 s. It is found that it is feasible to electrochemically trigger/control the SI-ATRP and the polymerization rate is correlated to the potential applied to the gold chip. This work reveals important kinetic information for eSI-ATRP and offers a powerful platform for in situ investigation of such complicated processes.

  5. In situ development of self-reinforced cellulose nanocrystals based thermoplastic elastomers by atom transfer radical polymerization.

    Science.gov (United States)

    Yu, Juan; Wang, Chunpeng; Wang, Jifu; Chu, Fuxiang

    2016-05-05

    Recently, the utilization of cellulose nanocrystals (CNCs) as a reinforcing material has received a great attention due to its high elastic modulus. In this article, a novel strategy for the synthesis of self-reinforced CNCs based thermoplastic elastomers (CTPEs) is presented. CNCs were first surface functionalized with an initiator for surface-initiated atom transfer radical polymerization (SI-ATRP). Subsequently, SI-ATRP of methyl methacrylate (MMA) and butyl acrylate (BA) was carried out in the presence of sacrificial initiator to form CTPEs in situ. The CTPEs together with the simple blends of CNCs and linear poly(MMA-co-BA) copolymer (P(MMA-co-BA)) were characterized for comparative study. The results indicated that P(MMA-co-BA) was successfully grafted onto the surface of CNCs and the compatibility between CNCs and the polymer matrix in CTPEs was greatly enhanced. Specially, the CTPEs containing 2.15wt% CNCs increased Tg by 19.2°C and tensile strength by 100% as compared to the linear P(MMA-co-BA). Copyright © 2016 Elsevier Ltd. All rights reserved.

  6. A peroxidase mimic with atom transfer radical polymerization activity constructed through the grafting of heme onto metal-organic frameworks.

    Science.gov (United States)

    Jiang, Wei; Pan, Yue; Yang, Jiebing; Liu, Yong; Yang, Yan; Tang, Jun; Li, Quanshun

    2018-07-01

    Atom transfer radical polymerization (ATRP) has been considered to be an efficient strategy for constructing functional macromolecules owing to its simple operation and versatile monomers, and thus it is of great significance to develop ideal catalysts with higher activity and perfect reusability. We constructed a peroxidase mimic through the grafting of heme onto metal-organic frameworks UiO-66-NH 2 (ZrMOF), namely Heme-ZrMOF. After the systematic characterization of structure, the composite Heme-ZrMOF was demonstrated to possess high peroxidase activity using 2,2'-azinobis-(3-ethylbenzthiazoline-6-sulphonate) and 3,3',5,5'-tetramethylbenzidine as substrates. The enzyme mimic was then used as catalysts in the ATRP reactions of different monomers, in which favorable monomer conversion (44.6-98.0%) and product molecular weight (8600-25,600 g/mol) could be obtained. Compared to free heme, Heme-ZrMOF could efficiently achieve the easy separation of heme from the catalytic system and facilitate the ATRP reaction in an aqueous environment to avoid the utilization of organic solvents. In conclusion, the enzyme mimic Heme-ZrMOF could be potentially used as an effective catalyst for preparing well-defined polymers with biomedical applications. Copyright © 2018 Elsevier Inc. All rights reserved.

  7. Study of the metastable singlet of molecular nitrogen and of oxygen atoms in discharges and post-discharges

    International Nuclear Information System (INIS)

    Magne, Lionel

    1991-01-01

    Whereas discharges in nitrogen, in oxygen and in their mixtures are used in many different industrial processes (surface treatment, nitridation, oxidation, and so on), in order to get a better knowledge on nitrogen electronic states, this research thesis reports the study of the metastable singlet state of molecular nitrogen, and of oxygen atoms in their fundamental state. The molecular metastable has been observed by far-UV optical emission spectroscopy, in the positive column of a continuous discharge and in time post-discharge. As far as continuous discharge is concerned, the author measured the vibrational distribution of this state. A kinetic model has been developed, and calculated vibrational distributions are in good agreement with measurements. The density of oxygen atoms in fundamental state in time post-discharge has been measured by far-UV absorption optical spectroscopy. The probability of atom re-association of glass walls is deduced from the obtained results [fr

  8. The Dependence of Atomic Oxygen Undercutting of Protected Polyimide Kapton(tm) H upon Defect Size

    Science.gov (United States)

    Snyder, Aaron; deGroh, Kim K.

    2001-01-01

    Understanding the behavior of polymeric materials when exposed to the low-Earth-orbit (LEO) environment is important in predicting performance characteristics such as in-space durability. Atomic oxygen (AO) present in LEO is known to be the principal agent in causing undercutting erosion of SiO(x) protected polyimide Kapton(R) H film, which serves as a mechanically stable blanket material in solar arrays. The rate of undercutting is dependent on the rate of arrival, directionality and energy of the AO with respect to the film surface. The erosion rate also depends on the distribution of the size of defects existing in the protective coating. This paper presents results of experimental ground testing using low energy, isotropic AO flux together with numerical modeling to determine the dependence of undercutting erosion upon defect size.

  9. Atomic Oxygen Treatment Technique for Removal of Smoke Damage from Paintings

    Science.gov (United States)

    Rutledge, S. K.; Banks, B. A.

    1997-01-01

    Soot deposits that can accumulate on surfaces of a painting during a fire can be difficult to clean from some types of paintings without damaging the underlying paint layers. A non-contact technique has been developed which can remove the soot by allowing a gas containing atomic oxygen to flow over the surface and chemically react with the soot to form carbon monoxide and carbon dioxide. The reaction is limited to the surface, so the underlying paint is not touched. The process can be controlled so that the cleaning can be stopped once the paint surface is reached. This paper describes the smoke exposure and cleaning of untreated canvas, acrylic gesso, and sections of an oil painting using this technique. The samples were characterized by optical microscopy and reflectance spectroscopy.

  10. Chemical reactivity of hydrogen, nitrogen, and oxygen atoms at temperatures below 100 k

    Science.gov (United States)

    Mcgee, H. A., Jr.

    1973-01-01

    The synthesis of unusual compounds by techniques employing cryogenic cooling to retard their very extreme reactivity was investigated. Examples of such species that were studied are diimide (N2H2), cyclobutadiene (C4H4), cyclopropanone (C3H4O), oxirene (C2H2O), and many others. Special purpose cryogenically cooled inlet arrangements were designed such that the analyses incurred no warm-up of the cold, and frequently explosively unstable, compounds. Controlled energy electron impact techniques were used to measure critical potentials and to develop the molecular energetics and thermodynamics of these molecules and to gain some insight into their kinetic characteristics as well. Three and four carbon strained ring molecules were studied. Several reactions of oxygen and hydrogen atoms with simple molecules of H, N, C, and O in hard quench configurations were studied. And the quench stabilization of BH3 was explored as a model system in cryochemistry.

  11. Ground-Laboratory to In-Space Atomic Oxygen Correlation for the Polymer Erosion and Contamination Experiment (PEACE) Polymers

    Science.gov (United States)

    Stambler, Arielle H.; Inoshita, Karen E.; Roberts, Lily M.; Barbagallo, Claire E.; deGroh, Kim K.; Banks, Bruce A.

    2011-01-01

    The Materials International Space Station Experiment 2 (MISSE 2) Polymer Erosion and Contamination Experiment (PEACE) polymers were exposed to the environment of low Earth orbit (LEO) for 3.95 years from 2001 to 2005. There were 41 different PEACE polymers, which were flown on the exterior of the International Space Station (ISS) in order to determine their atomic oxygen erosion yields. In LEO, atomic oxygen is an environmental durability threat, particularly for long duration mission exposures. Although spaceflight experiments, such as the MISSE 2 PEACE experiment, are ideal for determining LEO environmental durability of spacecraft materials, ground-laboratory testing is often relied upon for durability evaluation and prediction. Unfortunately, significant differences exist between LEO atomic oxygen exposure and atomic oxygen exposure in ground-laboratory facilities. These differences include variations in species, energies, thermal exposures and radiation exposures, all of which may result in different reactions and erosion rates. In an effort to improve the accuracy of ground-based durability testing, ground-laboratory to in-space atomic oxygen correlation experiments have been conducted. In these tests, the atomic oxygen erosion yields of the PEACE polymers were determined relative to Kapton H using a radio-frequency (RF) plasma asher (operated on air). The asher erosion yields were compared to the MISSE 2 PEACE erosion yields to determine the correlation between erosion rates in the two environments. This paper provides a summary of the MISSE 2 PEACE experiment; it reviews the specific polymers tested as well as the techniques used to determine erosion yield in the asher, and it provides a correlation between the space and ground laboratory erosion yield values. Using the PEACE polymers asher to in-space erosion yield ratios will allow more accurate in-space materials performance predictions to be made based on plasma asher durability evaluation.

  12. Dependence of atomic oxygen resistance and the tribological properties on microstructures of WS2 films

    International Nuclear Information System (INIS)

    Xu, Shusheng; Gao, Xiaoming; Hu, Ming; Sun, Jiayi; Jiang, Dong; Wang, Desheng; Zhou, Feng; Weng, Lijun; Liu, Weimin

    2014-01-01

    Graphical abstract: - Highlights: • Pure WS 2 and WS 2 -Al composite films with different structures were prepared. • The compactness of WS 2 film was significantly improved due to incorporation of Al. • Different mechanisms of atomic oxygen resistance of both the films were discussed. • Films before and after AO irradiation kept the unchanged tribological properties. • The composite films showed much better wear resistance than pure WS 2 film. - Abstract: To study the anti-oxidation mechanism of WS 2 films, the pure WS 2 , and Al doped WS 2 composite films were prepared via radio frequency sputtering and the atomic oxygen (AO) irradiation tests were conducted using a ground AO simulation facility. The tribological properties of both films before and after AO irradiation were evaluated using vacuum ball-on-disk tribo-tester. The incorporation of a small fraction of Al dopant resulted in microstructure change from loose columnar platelet with significant porosity for pure WS 2 film to very dense structure. In pure WS 2 film, WS 2 exists as crystalline phase with edge-plane preferential orientation, but nanocrystalline and amorphous phase coexists for the WS 2 -Al composite film. Even if large amount of AO transported into the interior through the longitudinal pores, the pure film showed good AO irradiation resistance owing to the basal plane of WS 2 crystal exhibiting much higher anti-oxidation capacity than the edge-plane. The composite film also had excellent AO irradiation resistance due to the formation of effective thinner WO 3 cladding layer in the sub-surface layer. Tribological results revealed that the composite films showed a significantly improved wear resistance, in comparison to the pure WS 2 film. Besides, due to the effective AO resistance, the tribological properties of WS 2 films remained almost unchanged before and after AO irradiation

  13. Lipid nanocarriers based on natural oils with high activity against oxygen free radicals and tumor cell proliferation

    International Nuclear Information System (INIS)

    Lacatusu, I.; Badea, N.; Badea, G.; Oprea, O.; Mihaila, M.A.; Kaya, D.A.; Stan, R.; Meghea, A.

    2015-01-01

    The development of nano-dosage forms of phytochemicals represents a significant progress of the scientific approach in the biomedical research. The aim of this study was to assess the effectiveness of lipid nanocarriers based on natural oils (grape seed oil, fish oil and laurel leaf oil) in counteracting free radicals and combating certain tumor cells. No drug was encapsulated in the nanocarriers. The cytotoxic effect exerted by bioactive nanocarriers against two tumor cells, MDA-MB 231 and HeLa cell lines, and two normal cells, L929 and B16 cell lines, was measured using the MTT assay, while oxidative damage was assessed by measuring the total antioxidant activity using chemiluminescence analysis. The best performance was obtained for nanocarriers based on an association of grape seed and laurel leaf oils, with a capacity to scavenge about 98% oxygen free radicals. A dose of nanocarriers of 5 mg·mL −1 has led to a drastic decrease in tumor cell proliferation even in the absence of an antitumor drug (e.g. about 50% viability for MDA-MB 231 cell line and 60% viability for HeLa cell line). A comparative survival profile of normal and tumor cells, which were exposed to an effective dose of 2.5 mg·mL −1 lipid nanocarriers, has revealed a death rate of 20% for normal B16 cells and of 40% death rate for MDA-MB 231 and HeLa tumor cells. The results in this study imply that lipid nanocarriers based on grape seed oil in association with laurel leaf oil could be a candidate to reduce the delivery system toxicity and may significantly improve the therapeutic efficacy of antitumor drugs in clinical applications. - Highlights: • Functional lipid nanocarriers with unique features and broad spectrum effectiveness • Lipid nanocarriers based on laureal leaf oil (LLO) and grape seed oil (GSO) • Antioxidant activity has reached 98% for nanocarriers containing 25% GSO and 2% LLO. • LLO exerts a significant cytotoxic effect against HeLa and MDA-MB 231 tumor cells. • 50

  14. Lipid nanocarriers based on natural oils with high activity against oxygen free radicals and tumor cell proliferation

    Energy Technology Data Exchange (ETDEWEB)

    Lacatusu, I.; Badea, N.; Badea, G.; Oprea, O. [University Politehnica of Bucharest, Faculty of Applied Chemistry and Materials Science, Polizu Street No 1, 011061 Bucharest (Romania); Mihaila, M.A. [Institute of Virusology “Stefan S. Nicolau”, Center of Immunology, Bravu Road, No. 285, 030304 Bucharest (Romania); Kaya, D.A. [Department of Field Crops, Faculty of Agriculture, Mustafa Kemal University, 31030 Antakya, Hatay (Turkey); Stan, R., E-mail: rl_stan2000@yahoo.com [University Politehnica of Bucharest, Faculty of Applied Chemistry and Materials Science, Polizu Street No 1, 011061 Bucharest (Romania); Meghea, A. [University Politehnica of Bucharest, Faculty of Applied Chemistry and Materials Science, Polizu Street No 1, 011061 Bucharest (Romania)

    2015-11-01

    The development of nano-dosage forms of phytochemicals represents a significant progress of the scientific approach in the biomedical research. The aim of this study was to assess the effectiveness of lipid nanocarriers based on natural oils (grape seed oil, fish oil and laurel leaf oil) in counteracting free radicals and combating certain tumor cells. No drug was encapsulated in the nanocarriers. The cytotoxic effect exerted by bioactive nanocarriers against two tumor cells, MDA-MB 231 and HeLa cell lines, and two normal cells, L929 and B16 cell lines, was measured using the MTT assay, while oxidative damage was assessed by measuring the total antioxidant activity using chemiluminescence analysis. The best performance was obtained for nanocarriers based on an association of grape seed and laurel leaf oils, with a capacity to scavenge about 98% oxygen free radicals. A dose of nanocarriers of 5 mg·mL{sup −1} has led to a drastic decrease in tumor cell proliferation even in the absence of an antitumor drug (e.g. about 50% viability for MDA-MB 231 cell line and 60% viability for HeLa cell line). A comparative survival profile of normal and tumor cells, which were exposed to an effective dose of 2.5 mg·mL{sup −1} lipid nanocarriers, has revealed a death rate of 20% for normal B16 cells and of 40% death rate for MDA-MB 231 and HeLa tumor cells. The results in this study imply that lipid nanocarriers based on grape seed oil in association with laurel leaf oil could be a candidate to reduce the delivery system toxicity and may significantly improve the therapeutic efficacy of antitumor drugs in clinical applications. - Highlights: • Functional lipid nanocarriers with unique features and broad spectrum effectiveness • Lipid nanocarriers based on laureal leaf oil (LLO) and grape seed oil (GSO) • Antioxidant activity has reached 98% for nanocarriers containing 25% GSO and 2% LLO. • LLO exerts a significant cytotoxic effect against HeLa and MDA-MB 231 tumor

  15. Investigation of the Mechanism of Electron Capture and Electron Transfer Dissociation of Peptides with a Covalently Attached Free Radical Hydrogen Atom Scavenger.

    Science.gov (United States)

    Sohn, Chang Ho; Yin, Sheng; Peng, Ivory; Loo, Joseph A; Beauchamp, J L

    2015-11-15

    The mechanisms of electron capture and electron transfer dissociation (ECD and ETD) are investigated by covalently attaching a free-radical hydrogen atom scavenger to a peptide. The 2,2,6,6-tetramethylpiperidin-l-oxyl (TEMPO) radical was chosen as the scavenger due to its high hydrogen atom affinity (ca. 280 kJ/mol) and low electron affinity (ca. 0.45 ev), and was derivatized to the model peptide, FQX TEMPO EEQQQTEDELQDK. The X TEMPO residue represents a cysteinyl residue derivatized with an acetamido-TEMPO group. The acetamide group without TEMPO was also examined as a control. The gas phase proton affinity (882 kJ/mol) of TEMPO is similar to backbone amide carbonyls (889 kJ/mol), minimizing perturbation to internal solvation and sites of protonation of the derivatized peptides. Collision induced dissociation (CID) of the TEMPO tagged peptide dication generated stable odd-electron b and y type ions without indication of any TEMPO radical induced fragmentation initiated by hydrogen abstraction. The type and abundance of fragment ions observed in the CID spectra of the TEMPO and acetamide tagged peptides are very similar. However, ECD of the TEMPO labeled peptide dication yielded no backbone cleavage. We propose that a labile hydrogen atom in the charge reduced radical ions is scavenged by the TEMPO radical moiety, resulting in inhibition of N-C α backbone cleavage processes. Supplemental activation after electron attachment (ETcaD) and CID of the charge-reduced precursor ion generated by electron transfer of the TEMPO tagged peptide dication produced a series of b + H (b H ) and y + H (y H ) ions along with some c ions having suppressed intensities, consistent with stable O-H bond formation at the TEMPO group. In summary, the results indicate that ECD and ETD backbone cleavage processes are inhibited by scavenging of a labile hydrogen atom by the localized TEMPO radical moiety. This observation supports the conjecture that ECD and ETD processes involve long

  16. Single Atomic Iron Catalysts for Oxygen Reduction in Acidic Media: Particle Size Control and Thermal Activation

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Hanguang; Hwang, Sooyeon; Wang, Maoyu; Feng, Zhenxing; Karakalos, Stavros; Luo, Langli; Qiao, Zhi; Xie, Xiaohong; Wang, Chongmin; Su, Dong; Shao, Yuyan; Wu, Gang (BNL); (Oregon State U.); (SC); (PNNL); (Buffalo)

    2017-09-26

    It remains a grand challenge to replace platinum group metal (PGM) catalysts with earth-abundant materials for the oxygen reduction reaction (ORR) in acidic media, which is crucial for large-scale deployment of proton exchange membrane fuel cells (PEMFCs). Here, we report a high-performance atomic Fe catalyst derived from chemically Fe-doped zeolitic imidazolate frameworks (ZIFs) by directly bonding Fe ions to imidazolate ligands within 3D frameworks. Although the ZIF was identified as a promising precursor, the new synthetic chemistry enables the creation of well-dispersed atomic Fe sites embedded into porous carbon without the formation of aggregates. The size of catalyst particles is tunable through synthesizing Fe-doped ZIF nanocrystal precursors in a wide range from 20 to 1000 nm followed by one-step thermal activation. Similar to Pt nanoparticles, the unique size control without altering chemical properties afforded by this approach is able to increase the number of PGM-free active sites. The best ORR activity is measured with the catalyst at a size of 50 nm. Further size reduction to 20 nm leads to significant particle agglomeration, thus decreasing the activity. Using the homogeneous atomic Fe model catalysts, we elucidated the active site formation process through correlating measured ORR activity with the change of chemical bonds in precursors during thermal activation up to 1100 °C. The critical temperature to form active sites is 800 °C, which is associated with a new Fe species with a reduced oxidation number (from Fe3+ to Fe2+) likely bonded with pyridinic N (FeN4) embedded into the carbon planes. Further increasing the temperature leads to continuously enhanced activity, linked to the rise of graphitic N and Fe–N species. The new atomic Fe catalyst has achieved respectable ORR activity in challenging acidic media (0.5 M H2SO4), showing a half-wave potential of 0.85 V vs RHE and leaving only a 30 mV gap with Pt/C (60 μgPt/cm2). Enhanced stability

  17. Quartz-crystal microbalance study for characterizing atomic oxygen in plasma ash tools

    International Nuclear Information System (INIS)

    Srivastava, A.K.; Sakthivel, P.

    2001-01-01

    This article discusses the measurement of atomic oxygen (AO) concentrations in an oxygen discharge using a quartz-crystal microbalance (QCM). This is a device that has been previously used for monitoring thin-film deposition, among several other applications. The sensor consists of a silver-coated quartz crystal that oscillates at its specific resonant frequency (typically, at about 6 MHz), which is dependent on the mass of the crystal. When exposed to AO, the silver oxidizes rapidly, resulting in a change in its mass, and a consequent change in this frequency. The frequency change is measured with a counter, and when plotted versus time, it may be fit to a standard diffusion-limited oxide-growth model. This model is then used to determine the specific AO flux to the crystal, and by inference, to the wafer. Initial results of QCM measurements in the FusionGemini Plasma Asher (GPL TM -standard downstream microwave asher) and FusionGemini Enhanced Strip (GES TM -fluorine compatible enhanced strip asher) are presented in this article. The results indicate AO densities of the order of 10 12 cm -3 on the wafer. There is a marked increase in AO concentration with addition of nitrogen into the plasma, and a decrease in AO concentration with increasing pressure at constant flow. Effects of increasing the total plasma volume in the enhanced strip tool on AO production are discussed

  18. Oxygen atom transfer reactions from Mimoun complexes to sulfides and sulfoxides. A bonding evolution theory analysis.

    Science.gov (United States)

    González-Navarrete, Patricio; Sensato, Fabricio R; Andrés, Juan; Longo, Elson

    2014-08-07

    In this research, a comprehensive theoretical investigation has been conducted on oxygen atom transfer (OAT) reactions from Mimoun complexes to sulfides and sulfoxides. The joint use of the electron localization function (ELF) and Thom's catastrophe theory (CT) provides a powerful tool to analyze the evolution of chemical events along a reaction pathway. The progress of the reaction has been monitored by structural stability domains from ELF topology while the changes between them are controlled by turning points derived from CT which reveal that the reaction mechanism can be separated in several steps: first, a rupture of the peroxo O1-O2 bond, then a rearrangement of lone pairs of the sulfur atom occurs and subsequently the formation of S-O1 bond. The OAT process involving the oxidation of sulfides and sulfoxides is found to be an asynchronous process where O1-O2 bond breaking and S-O1 bond formation processes do not occur simultaneously. Nucleophilic/electrophilic characters of both dimethyl sulfide and dimethyl sulfoxide, respectively, are sufficiently described by our results, which hold the key to unprecedented insight into the mapping of electrons that compose the bonds while the bonds change.

  19. Multiple ionization and coupling effects in L-subshell ionization of heavy atoms by oxygen ions

    International Nuclear Information System (INIS)

    Pajek, M.; Banas, D.; Semaniak, J.; Braziewicz, J.; Majewska, U.; Chojnacki, S.; Czyzewski, T.; Fijal, I.; Jaskola, M.; Glombik, A.; Kretschmer, W.; Trautmann, D.; Lapicki, G.; Mukoyama, T.

    2003-01-01

    The multiple-ionization and coupling effects in L-shell ionization of atoms by heavy-ion impact have been studied by measuring the L x-ray production cross sections in solid targets of Au, Bi, Th, and U bombarded by oxygen ions in the energy range 6.4-70 MeV. The measured L x-ray spectra were analyzed using the recently proposed method accounting for the multiple-ionization effects, such as x-ray line shifting and broadening, which enables one to obtain the ionization probabilities for outer shells. The L-subshell ionization cross sections have been obtained from measured x-ray production cross sections for resolved Lα 1,2 , Lγ 1 , and Lγ 2,3 transitions using the L-shell fluorescence and Coster-Kronig yields being substantially modified by the multiple ionization in the M and N shells. In particular, the effect of closing of strong L 1 -L 3 M 4,5 Coster-Kronig transitions in multiple-ionized atoms was evidenced and discussed. The experimental ionization cross sections for the L 1 , L 2 , and L 3 subshells have been compared with the predictions of the semiclassical approximation (SCA) and the ECPSSR theory that includes the corrections for the binding-polarization effect within the perturbed stationary states approximation, the projecticle energy loss, and Coulomb deflection effects as well as the relativistic description of inner-shell electrons. These approaches were further modified to include the L-subshell couplings within the ''coupled-subshell model'' (CSM). Both approaches, when modified for the coupling effects, are in better agreement with the data. Particularly, the predictions of the SCA-CSM calculations reproduce the experimental L-subshell ionization cross section reasonably well. Remaining discrepancies are discussed qualitatively, in terms of further modifications of the L-shell decay rates caused by a change of electronic wave functions in multiple-ionized atoms

  20. Effect of Rubia cordifolia, Fagonia cretica linn, and Tinospora cordifolia on free radical generation and lipid peroxidation during oxygen-glucose deprivation in rat hippocampal slices

    International Nuclear Information System (INIS)

    Rawal, Avinash; Muddeshwar, Manohar; Biswas, Saibal

    2004-01-01

    The major damaging factor during and after the ischemic/hypoxic insult is the generation of free radicals, which leads to apoptosis, necrosis, and ultimately cell death. Rubia cordifolia (RC), Fagonia cretica linn (FC), and Tinospora cordifolia (TC) have been reported to contain a wide variety of antioxidants and have been in use in the eastern system of medicine for various disorders. Hippocampal slices were subjected to oxygen-glucose deprivation (OGD) and divided into three groups, control, OGD, and OGD+drug treated. Cytosolic reduced glutathione (GSH), nitric oxide [NO, measured as nitrite (NO 2 )]. EPR was used to establish the antioxidant effect of RC, FC, and TC with respect to superoxide anion (O2-), hydroxyl radicals (OH), nitric oxide (NO) radical, and peroxynitrite anion (ONOO - ) generated from pyrogallol, menadione, DETA-NO, and Sin-1, respectively. RT-PCR was performed for the three herbs to assess their effect on the expression of γ-glutamylcysteine ligase (GCLC), iNOS, and GAPDH gene expression. All the three herbs were effective in elevating the GSH levels and expression of the GCLC. The herbs also exhibited strong free radical scavenging properties against reactive oxygen and nitrogen species as revealed by electron paramagnetic resonance spectroscopy, diminishing the expression of iNOS gene. RC, FC, and TC therefore attenuate oxidative stress mediated cell injury during OGD and exert the above effects at both the cytosolic as well as at gene expression levels and may be effective therapeutic tool against ischemic brain damage

  1. Cyclosporine treatment reduces oxygen free radical generation and oxidative stress in the brain of hypoxia-reoxygenated newborn piglets.

    Directory of Open Access Journals (Sweden)

    Richdeep S Gill

    Full Text Available Oxygen free radicals have been implicated in the pathogenesis of hypoxic-ischemic encephalopathy. It has previously been shown in traumatic brain injury animal models that treatment with cyclosporine reduces brain injury. However, the potential neuroprotective effect of cyclosporine in asphyxiated neonates has yet to be fully studied. Using an acute newborn swine model of hypoxia-reoxygenation, we evaluated the effects of cyclosporine on the brain, focusing on hydrogen peroxide (H(2O(2 production and markers of oxidative stress. Piglets (1-4 d, 1.4-2.5 kg were block-randomized into three hypoxia-reoxygenation experimental groups (2 h hypoxia followed by 4 h reoxygenation (n = 8/group. At 5 min after reoxygenation, piglets were given either i.v. saline (placebo, controls or cyclosporine (2.5 or 10 mg/kg i.v. bolus in a blinded-randomized fashion. An additional sham-operated group (n = 4 underwent no hypoxia-reoxygenation. Systemic hemodynamics, carotid arterial blood flow (transit-time ultrasonic probe, cerebral cortical H(2O(2 production (electrochemical sensor, cerebral tissue glutathione (ELISA and cytosolic cytochrome-c (western blot levels were examined. Hypoxic piglets had cardiogenic shock (cardiac output 40-48% of baseline, hypotension (mean arterial pressure 27-31 mmHg and acidosis (pH 7.04 at the end of 2 h of hypoxia. Post-resuscitation cyclosporine treatment, particularly the higher dose (10 mg/kg, significantly attenuated the increase in cortical H(2O(2 concentration during reoxygenation, and was associated with lower cerebral oxidized glutathione levels. Furthermore, cyclosporine treatment significantly attenuated the increase in cortical cytochrome-c and lactate levels. Carotid blood arterial flow was similar among groups during reoxygenation. Conclusively, post-resuscitation administration of cyclosporine significantly attenuates H(2O(2 production and minimizes oxidative stress in newborn piglets following hypoxia-reoxygenation.

  2. Improving the Characteristics of Sn-doped In{sub 2}O{sub 2} Grown at Room Temperature with Oxygen Radical-Assisted Electron Beam Deposition

    Energy Technology Data Exchange (ETDEWEB)

    Oh, Min-Suk [Korea Institute of Industrial Technology, Gwangju (Korea, Republic of); Seo, Inseok [Chonbuk National University, Jeonju (Korea, Republic of)

    2017-07-15

    Sn-doped In{sub 2}O{sub 3} (Indium tin oxide, ITO) is widely utilized in numerous industrial applications due to its high electrical conductivity and high optical transmittance in the visible region. High quality ITO thin-films have been grown at room temperature by oxygen radical assisted e-beam evaporation without any post annealing or plasma treatment. The introduction of oxygen radicals during e-beam growth greatly improved the surface morphology and structural properties of the ITO films. The obtained ITO film exhibits higher carrier mobility of 43.2 cm{sup 2}/V·s and larger optical transmittance of 84.6%, resulting in a higher figure of merit of ∼ 2.8 × 10{sup −2} Ω{sup −1}, which are quite comparable to the ITO film deposited by conventional e-beam evaporation. These results show that ITO films grown by oxygen radical assisted e-beam evaporation at room temperature with high optical transmittance and high electron conductivity have a great potential for organic optoelectronic devices.

  3. Improving the characteristics of Sn-doped In2O2 grown at room temperature with oxygen radical-assisted electron beam deposition

    Science.gov (United States)

    Oh, Min-Suk; Seo, Inseok

    2017-07-01

    Sn-doped In2O3 (Indium tin oxide, ITO) is widely utilized in numerous industrial applications due to its high electrical conductivity and high optical transmittance in the visible region. High quality ITO thin-films have been grown at room temperature by oxygen radical assisted e-beam evaporation without any post annealing or plasma treatment. The introduction of oxygen radicals during e-beam growth greatly improved the surface morphology and structural properties of the ITO films. The obtained ITO film exhibits higher carrier mobility of 43.2 cm2/V·s and larger optical transmittance of 84.6%, resulting in a higher figure of merit of ˜ 2.8 × 10-2 Ω-1, which are quite comparable to the ITO film deposited by conventional e-beam evaporation. These results show that ITO films grown by oxygen radical assisted e-beam evaporation at room temperature with high optical transmittance and high electron conductivity have a great potential for organic optoelectronic devices.

  4. Correlation among Singlet-Oxygen Quenching, Free-Radical Scavenging, and Excited-State Intramolecular-Proton-Transfer Activities in Hydroxyflavones, Anthocyanidins, and 1-Hydroxyanthraquinones.

    Science.gov (United States)

    Nagaoka, Shin-Ichi; Bandoh, Yuki; Nagashima, Umpei; Ohara, Keishi

    2017-10-26

    Singlet-oxygen ( 1 O 2 ) quenching, free-radical scavenging, and excited-state intramolecular proton-transfer (ESIPT) activities of hydroxyflavones, anthocyanidins, and 1-hydroxyanthraquinones were studied by means of laser, stopped-flow, and steady-state spectroscopies. In hydroxyflavones and anthocyanidins, the 1 O 2 quenching activity positively correlates to the free-radical scavenging activity. The reason for this correlation can be understood by considering that an early step of each reaction involves electron transfer from the unfused phenyl ring (B-ring), which is singly bonded to the bicyclic chromen or chromenylium moiety (A- and C-rings). Substitution of an electron-donating OH group at B-ring enhances the electron transfer leading to activation of the 1 O 2 quenching and free-radical scavenging. In 3-hydroxyflavones, the OH substitution at B-ring reduces the activity of ESIPT within C-ring, which can be explained in terms of the nodal-plane model. As a result, the 1 O 2 quenching and free-radical scavenging activities negatively correlate to the ESIPT activity. A catechol structure at B-ring is another factor that enhances the free-radical scavenging in hydroxyflavones. In contrast to these hydroxyflavones, 1-hydroxyanthraquinones having an electron-donating OH substituent adjacent to the O-H---O═C moiety susceptible to ESIPT do not show a simple correlation between their 1 O 2 quenching and ESIPT activities, because the OH substitution modulates these reactions.

  5. Effect of oxygen atoms dissociated by non-equilibrium plasma on flame of methane oxygen and argon pre-mixture gas

    Science.gov (United States)

    Akashi, Haruaki; Yoshinaga, Tomokazu; Sasaki, Koichi

    2014-10-01

    For more efficient way of combustion, plasma-assisted combustion has been investigated by many researchers. But it is very difficult to clarify the effect of plasma even on the flame of methane. Because there are many complex chemical reactions in combustion system. Sasaki et al. has reported that the flame length of methane and air premixed burner shortened by irradiating microwave power. They also measured emission from Second Positive Band System of nitrogen during the irradiation. The emission indicates existence of high energy electrons which are accelerated by the microwave. The high energy electrons also dissociate oxygen molecules easily and oxygen atom would have some effects on the flame. But the dissociation ratio of oxygen molecules by the non-equilibrium plasma is significantly low, compared to that in the combustion reaction. To clarify the effect of dissociated oxygen atoms on the flame, dependence of dissociation ratio of oxygen on the flame has been examined using CHEMKIN. It is found that in the case of low dissociation ratio of 10-6, the ignition of the flame becomes slightly earlier. It is also found that in the case of high dissociation ratio of 10-3, the ignition time becomes significantly earlier by almost half. This work was supported by KAKENHI (22340170).

  6. Synthesis of Well-Defined Three-Arm Star-Branched Polystyrene through Arm-First Coupling Approach by Atom Transfer Radical Polymerization

    OpenAIRE

    Shahabuddin, Syed; Hamime Ismail, Fatem; Mohamad, Sharifah; Muhamad Sarih, Norazilawati

    2015-01-01

    Here we describe a simple route to synthesize three-arm star-branched polystyrene. Atom transfer radical polymerization technique has been utilized to yield branched polystyrene involving Williamson coupling strategy. Initially a linear polymeric chain of predetermined molecular weight has been synthesized which is further end-functionalized into a primary alkyl bromide moiety, a prime requisition for Williamson reaction. The end-functionalized polymer is then coupled using 1,1,1-tris(4-hydro...

  7. Light element atom, molecule and radical behaviour in the divertor and edge plasma regions. Summary report of the 1. research coordination meeting

    International Nuclear Information System (INIS)

    Braams, B.J.

    2010-01-01

    The first research coordination meeting of the Coordinated Research Project (CRP) on Light Element Atom, Molecule and Radical Behaviour in the Divertor and Edge Plasma Regions was held 18-20 November 2009 at IAEA headquarters, bringing together experts representing 14 institutions. Participants summarized their recent and ongoing work pertinent to the research project. The specific objectives of the CRP and a detailed work plan were formulated. The discussions, conclusions and recommendations of the meeting are summarized in this report. (author)

  8. The potential of Cu(I)Cl/2,2'-bipyridine catalysis in a triblock copolymer preparation by atom transfer radical polymerization

    Czech Academy of Sciences Publication Activity Database

    Masař, Bohumil; Vlček, Petr; Kříž, Jaroslav

    2001-01-01

    Roč. 81, č. 14 (2001), s. 3514-3522 ISSN 0021-8995 R&D Projects: GA MŠk OC P1.10; GA AV ČR KSK2050602 Institutional research plan: CEZ:AV0Z4050913 Keywords : atom transfer radical polymerization * triblock copolymers * sequential synthesis Subject RIV: CD - Macromolecular Chemistry Impact factor: 0.992, year: 2001

  9. Atmospheric chemistry of trans-CF3CH=CHCl: Kinetics of the gas-phase reactions with Cl atoms, OH radicals, and O3

    DEFF Research Database (Denmark)

    Andersen, Mads Peter Sulbaek; Nilsson, Elna Johanna Kristina; Nielsen, Ole John

    2008-01-01

    Long path length Fourier transform infrared (FTIR)–smog chamber techniques were used to study the kinetics of the gas-phase reactions of Cl atoms, OH radicals and O3 with trans-3,3,3-trifluoro-1-chloropropene, t-CF3CH CHCl, in 700 Torr total pressure at 295±2K. Values of k(Cl + t-CF3CH CHCl) = (5...

  10. ESR investigation of the reactions of glutathione, cysteine and penicillamine thiyl radicals: competitive formation of RSOcenter dot, Rcenter dot, RSSRcenter dot-. , and RSScenter dot

    Energy Technology Data Exchange (ETDEWEB)

    Becker, David; Swarts, Steven; Champagne, Mark; Sevilla, M D

    1988-05-01

    The reactions of cysteine, glutathione and penicillamine thiyl radicals with oxygen and their parent thiols in frozen solutions have been elucidated with e.s.r. The major sulfur radicals observed are: (1) thiyl radicals, RS center dot; (2) disulfide radical anions, RSSR anion radicals; (3) perthiyl radicals, RSS center dot and upon introduction of oxygen; (4) sulfinyl radicals, RSO center dot, where R represents the remainder of the cysteine, glutathione or penicillamine moiety. The radical product observed depends on pH, concentration of thiol, and presence or absence of molecular oxygen. The sulfinyl radical is a ubiquitous intermediate, peroxyl radical attack on thiols may lead to sulfinyl radicals. The authors elaborate the observed reaction sequences that lead to sulfinyl radicals and, using /sup 17/O isotopic substitution studies, demonstrate the oxygen atom in sulfinyl radicals originates from dissolved molecular oxygen. The glutathione radical is found to abstract hydrogen from the ..cap alpha..-carbon position on the cysteine residue of glutathione to form a carbon-centred radical.

  11. Protein adsorption resistance of PVP-modified polyurethane film prepared by surface-initiated atom transfer radical polymerization

    Energy Technology Data Exchange (ETDEWEB)

    Yuan, Huihui; Qian, Bin; Zhang, Wei [Shanghai Key Laboratory of Functional Materials Chemistry and Research Center of Analysis and Test, East China University of Science and Technology, Shanghai 200237 (China); Lan, Minbo, E-mail: minbolan@ecust.edu.cn [Shanghai Key Laboratory of Functional Materials Chemistry and Research Center of Analysis and Test, East China University of Science and Technology, Shanghai 200237 (China); State Key Laboratory of Bioreactor Engineering, East China University of Science and Technology, Shanghai 200237 (China)

    2016-02-15

    Highlights: • Antifouling PVP brushes were successfully grafted on PU films by SI-ATRP. • The effect of polymerization time on surface property and topography was studied. • Hydrophilicity and protein fouling resistance of PVP–PU films were greatly promoted. • Competitive adsorption of three proteins on PVP–PU films was evaluated. - Abstract: An anti-fouling surface of polyurethane (PU) film grafted with Poly(N-vinylpyrrolidone) (PVP) was prepared through surface-initiated atom transfer radical polymerization (SI-ATRP). And the polymerization time was investigated to obtain PU films with PVP brushes of different lengths. The surface properties and protein adsorption of modified PU films were evaluated. The results showed that the hydrophilicity of PU–PVP films were improved with the increase of polymerization time, which was not positive correlation with the surface roughness due to the brush structure. Additionally, the protein resistance performance was promoted when prolonging the polymerization time. The best antifouling PU–PVP (6.0 h) film reduced the adsoption level of bovine serum albumin (BSA), lysozyme (LYS), and brovin serum fibrinogen (BFG) by 93.4%, 68.3%, 85.6%, respectively, compared to the unmodified PU film. The competitive adsorption of three proteins indicated that LYS preferentially adsorbed on the modified PU film, while BFG had the lowest adsorption selectivity. And the amount of BFG on PU–PVP (6.0 h) film reduced greatly to 0.08 μg/cm{sup 2}, which was almost one-tenth of its adsorption from the single-protein system. Presented results suggested that both hydrophilicity and surface roughness might be the important factors in all cases of protein adsorption, and the competitive or selective adsorption might be related to the size of the proteins, especially on the non-charged films.

  12. Protein adsorption resistance of PVP-modified polyurethane film prepared by surface-initiated atom transfer radical polymerization

    International Nuclear Information System (INIS)

    Yuan, Huihui; Qian, Bin; Zhang, Wei; Lan, Minbo

    2016-01-01

    Highlights: • Antifouling PVP brushes were successfully grafted on PU films by SI-ATRP. • The effect of polymerization time on surface property and topography was studied. • Hydrophilicity and protein fouling resistance of PVP–PU films were greatly promoted. • Competitive adsorption of three proteins on PVP–PU films was evaluated. - Abstract: An anti-fouling surface of polyurethane (PU) film grafted with Poly(N-vinylpyrrolidone) (PVP) was prepared through surface-initiated atom transfer radical polymerization (SI-ATRP). And the polymerization time was investigated to obtain PU films with PVP brushes of different lengths. The surface properties and protein adsorption of modified PU films were evaluated. The results showed that the hydrophilicity of PU–PVP films were improved with the increase of polymerization time, which was not positive correlation with the surface roughness due to the brush structure. Additionally, the protein resistance performance was promoted when prolonging the polymerization time. The best antifouling PU–PVP (6.0 h) film reduced the adsoption level of bovine serum albumin (BSA), lysozyme (LYS), and brovin serum fibrinogen (BFG) by 93.4%, 68.3%, 85.6%, respectively, compared to the unmodified PU film. The competitive adsorption of three proteins indicated that LYS preferentially adsorbed on the modified PU film, while BFG had the lowest adsorption selectivity. And the amount of BFG on PU–PVP (6.0 h) film reduced greatly to 0.08 μg/cm"2, which was almost one-tenth of its adsorption from the single-protein system. Presented results suggested that both hydrophilicity and surface roughness might be the important factors in all cases of protein adsorption, and the competitive or selective adsorption might be related to the size of the proteins, especially on the non-charged films.

  13. Reactive oxygen species-based measurement of the dependence of the Coulomb nanoradiator effect on proton energy and atomic Z value.

    Science.gov (United States)

    Seo, Seung-Jun; Jeon, Jae-Kun; Han, Sung-Mi; Kim, Jong-Ki

    2017-11-01

    The Coulomb nanoradiator (CNR) effect produces the dose enhancement effects from high-Z nanoparticles under irradiation with a high-energy ion beam. To gain insight into the radiation dose and biological significance of the CNR effect, the enhancement of reactive oxygen species (ROS) production from iron oxide or gold NPs (IONs or AuNPs, respectively) in water was investigated using traversing proton beams. The dependence of nanoradiator-enhanced ROS production on the atomic Z value and proton energy was investigated. Two biologically important ROS species were measured using fluorescent probes specific to •OH or [Formula: see text] in a series of water phantoms containing either AuNPs or IONs under irradiation with a 45- or 100-MeV proton beam. The enhanced generation of hydroxyl radicals (•OH) and superoxide anions ([Formula: see text]) was determined to be caused by the dependence on the NP concentration and proton energy. The proton-induced Au or iron oxide nanoradiators exhibited different ROS enhancement rates depending on the proton energy, suggesting that the CNR radiation varied. The curve of the superoxide anion production from the Au-nanoradiator showed strong non-linearity, unlike the linear behavior observed for hydroxyl radical production and the X-ray photoelectric nanoradiator. In addition, the 45-MeV proton-induced Au nanoradiator exhibited an ROS enhancement ratio of 8.54/1.50 ([Formula: see text] / •OH), similar to that of the 100-KeV X-ray photoelectric Au nanoradiator (7.68/1.46). The ROS-based detection of the CNR effect revealed its dependence on the proton beam energy, dose and atomic Z value and provided insight into the low-linear energy transfer (LET) CNR radiation, suggesting that these factors may influence the therapeutic efficacy via chemical reactivities, transport behaviors, and intracellular oxidative stress.

  14. Spatially and Temporally Resolved Atomic Oxygen Measurements in Short Pulse Discharges by Two Photon Laser Induced Fluorescence

    Science.gov (United States)

    Lempert, Walter; Uddi, Mruthunjaya; Mintusov, Eugene; Jiang, Naibo; Adamovich, Igor

    2007-10-01

    Two Photon Laser Induced Fluorescence (TALIF) is used to measure time-dependent absolute oxygen atom concentrations in O2/He, O2/N2, and CH4/air plasmas produced with a 20 nanosecond duration, 20 kV pulsed discharge at 10 Hz repetition rate. Xenon calibrated spectra show that a single discharge pulse creates initial oxygen dissociation fraction of ˜0.0005 for air like mixtures at 40-60 torr total pressure. Peak O atom concentration is a factor of approximately two lower in fuel lean (φ=0.5) methane/air mixtures. In helium buffer, the initially formed atomic oxygen decays monotonically, with decay time consistent with formation of ozone. In all nitrogen containing mixtures, atomic oxygen concentrations are found to initially increase, for time scales on the order of 10-100 microseconds, due presumably to additional O2 dissociation caused by collisions with electronically excited nitrogen. Further evidence of the role of metastable N2 is demonstrated from time-dependent N2 2^nd Positive and NO Gamma band emission spectroscopy. Comparisons with modeling predictions show qualitative, but not quantitative, agreement with the experimental data.

  15. Relative stability of radicals derived from artemisinin: A semiempirical and DFT study

    Science.gov (United States)

    Arantes, C.; de Araujo, M. T.; Taranto, A. G.; de M. Carneiro, J. W.

    The semiempirical AM1 and PM3 methods, as well as the density functional (DFT/B3LYP) approach using the 6-31g(d) basis set, were employed to calculate the relative stability of intermediate radicals derived from artemisinin, a sesquiterpene lactone having an endoperoxide bridge that is essential for its antimalarial activity. The compounds studied have their nonperoxidic oxygen atom of the trioxane ring and/or the carbonyl group replaced by a CH2 unit. Relative stabilities were calculated by means of isodesmic equations using artemisinin as reference. It was found that replacement of oxygen atoms decreases the relative stability of the anionic radical intermediates. In contrast, for compounds with inverted stereochemistry the intermediate radicals were found to be more stable than those with the artemisinin-like stereochemistry. These relative stabilities may modulate the antimalarial potency. Radicals centered on carbon are always more stable than the corresponding radicals centered on oxygen.

  16. Electronic excitation of Ti atoms sputtered by energetic Ar+ and He+ from clean and monolayer oxygen covered surfaces

    International Nuclear Information System (INIS)

    Pellin, M.J.; Gruen, D.M.; Young, C.E.; Wiggins, M.D.; Argonne National Lab., IL

    1983-01-01

    Electronic excitation of Ti atoms ejected during energetic ion bombardment (Ar + , He + ) of well characterized clean and oxygen covered polycrystalline Ti metal surfaces has been determined. For states with 0 to 2 eV and 3 to 5.5 eV of electronic energy, static mode laser fluorescence spectroscopy (LFS) and static mode spontaneous fluorescence spectroscopy (SFS) were used respectively. These experiments which were carried out in a UHV ( -10 Torr) system equipped with an Auger spectrometer provide measurements of the correlation between oxygen coverage (0 to 3 monolayers) and the excited state distribution of sputtered Ti atoms. The experimentally determined electronic partition function of Ti atoms does not show an exponential dependence on energy (E) above the ground state but rather an E -2 or E -3 power law dependence. (orig.)

  17. Single Atomic Iron Catalysts for Oxygen Reduction in Acidic Media: Particle Size Control and Thermal Activation

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Hanguang [Department; Hwang, Sooyeon [Center; Wang, Maoyu [School; Feng, Zhenxing [School; Karakalos, Stavros [Department; Luo, Langli [Pacific Northwest National Laboratory, Richland, Washington 99352, United States; Qiao, Zhi [Department; Xie, Xiaohong [Pacific Northwest National Laboratory, Richland, Washington 99352, United States; Wang, Chongmin [Pacific Northwest National Laboratory, Richland, Washington 99352, United States; Su, Dong [Center; Shao, Yuyan [Pacific Northwest National Laboratory, Richland, Washington 99352, United States; Wu, Gang [Department

    2017-09-26

    To significantly reduce the cost of proton exchange membrane (PEM) fuel cells, current Pt must be replaced by platinum-metal-group (PGM)-free catalysts for the oxygen reduction reaction (ORR) in acid. We report here a new class of high-performance atomic iron dispersed carbon catalysts through controlled chemical doping of iron ions into zinc-zeolitic imidazolate framework (ZIF), a type of metal-organic framework (MOF). The novel synthetic chemistry enables accurate size control of Fe-doped ZIF catalyst particles with a wide range from 20 to 1000 nm without changing chemical properties, which provides a great opportunity to increase the density of active sites that is determined by the particle size. We elucidated the active site formation mechanism by correlating the chemical and structural changes with thermal activation process for the conversion from Fe-N4 complex containing hydrocarbon networks in ZIF to highly active FeNx sites embedded into carbon. A temperature of 800oC was identified as the critical point to start forming pyridinic nitrogen doping at the edge of the graphitized carbon planes. Further increasing heating temperature to 1100oC leads to increase of graphitic nitrogen, generating possible synergistic effect with FeNx sites to promote ORR activity. The best performing catalyst, which has well-defined particle size around 50 nm and abundance of atomic FeNx sites embedded into carbon structures, achieve a new performance milestone for the ORR in acid including a half-wave potential of 0.85 V vs RHE and only 20 mV loss after 10,000 cycles in O2 saturated H2SO4 electrolyte. The new class PGM-free catalyst with approaching activity to Pt holds great promise for future PEM fuel cells.

  18. Kinetics and mechanisms of the reactions of alkyl radicals with oxygen and with complexes of Co(III), Ru(III), and Ni(III)

    International Nuclear Information System (INIS)

    Kelley, D.

    1990-01-01

    The kinetics of the reactions of C 2 H 5 radical with Co(NH 3 ) 5 X 2+ , Ru(NH 3 ) 5 X 2+ , and Co(dmgH) 2 (X) (Y) (X = Br, Cl, N 3 , SCN; Y = H 2 O, CH 3 CN) complexes were studied using laser flash photolysis of ethylcobalt complexes. The kinetics were obtained by the kinetic probe method. Some relative rate constants were also determined by a competition method based on ethyl halide product ratios. The kinetics of colligation reactions of a series of alkyl radicals with β-Ni(cyclam) 2+ were studied using flaser flash photolysis of alkylcobalt complexes. Again, the kinetics were obtained by employing the kinetic probe competition method. The kinetics of the unimolecular homolysis of a series of RNi(cyclam)H 2 O 2+ were studied. Activation parameters were obtained for the unimolecular homolysis of C 2 H 5 Ni(cyclam)H 2 O 2+ . Kinetic and thermodynamic data obtained from these reactions were compared with those for the σ-bonded organometallic complexes. The kinetics of the unimolecular homolysis of a series of RNi(cyclam)H 2 O 2+ complexes were studied by monitoring the formation of the oxygen insertion product RO 2 Ni(cyclam)H 2 O 2+ . The higher rate constants for the reactions of alkyl radicals with oxygen in solution, as compared with those measured in the gas phase, were discussed. 30 refs

  19. Unveiling the high-activity origin of single-atom iron catalysts for oxygen reduction reaction.

    Science.gov (United States)

    Yang, Liu; Cheng, Daojian; Xu, Haoxiang; Zeng, Xiaofei; Wan, Xin; Shui, Jianglan; Xiang, Zhonghua; Cao, Dapeng

    2018-06-26

    It is still a grand challenge to develop a highly efficient nonprecious-metal electrocatalyst to replace the Pt-based catalysts for oxygen reduction reaction (ORR). Here, we propose a surfactant-assisted method to synthesize single-atom iron catalysts (SA-Fe/NG). The half-wave potential of SA-Fe/NG is only 30 mV less than 20% Pt/C in acidic medium, while it is 30 mV superior to 20% Pt/C in alkaline medium. Moreover, SA-Fe/NG shows extremely high stability with only 12 mV and 15 mV negative shifts after 5,000 cycles in acidic and alkaline media, respectively. Impressively, the SA-Fe/NG-based acidic proton exchange membrane fuel cell (PEMFC) exhibits a high power density of 823 mW cm -2 Combining experimental results and density-functional theory (DFT) calculations, we further reveal that the origin of high-ORR activity of SA-Fe/NG is from the Fe-pyrrolic-N species, because such molecular incorporation is the key, leading to the active site increase in an order of magnitude which successfully clarifies the bottleneck puzzle of why a small amount of iron in the SA-Fe catalysts can exhibit extremely superior ORR activity.

  20. Carbon fiber CVD coating by carbon nanostructured for space materials protection against atomic oxygen

    Science.gov (United States)

    Pastore, Roberto; Bueno Morles, Ramon; Micheli, Davide

    2016-07-01

    In recent years, the emphasis in space research has been shifting from space exploration to commercialization of space. In order to utilize space for commercial purposes it is necessary to understand the low earth orbit (LEO) space environment where most of the activities will be carried out. The studies on the LEO environment are mainly focused towards understanding the effect of atomic oxygen (AO) on spacecraft materials. In the first few shuttle flights, materials looked frosty because they were actually being eroded and textured: AO reacts with organic materials on spacecraft exteriors, gradually damaging them. When a spacecraft travel in LEO (where crewed vehicles and the International Space Station fly), the AO formed from the residual atmosphere can react with the spacecraft surfaces, causing damage to the vehicle. Polymers are widely used in space vehicles and systems as structural materials, thermal blankets, thermal control coatings, conformal coatings, adhesives, lubricants, etc. Exposure of polymers and composites to the space environment may result in different detrimental effects via modification of their chemical, electrical, thermal, optical and mechanical properties as well as surface erosion. The major degradation effects in polymers are due to their exposure to atomic oxygen, vacuum ultraviolet and synergistic effects, which result in different damaging effects by modification of the polymer's chemical properties. In hydrocarbon containing polymers the main AO effect is the surface erosion via chemical reactions and the release of volatile reaction products associated with the mass loss. The application of a thin protective coating to the base materials is one of the most commonly used methods of preventing AO degradation. The purpose is to provide a barrier between base material and AO environment or, in some cases, to alter AO reactions to inhibit its diffusion. The effectiveness of a coating depends on its continuity, porosity, degree of

  1. Effects of Atomic Oxygen and Grease on Outgassing and Adhesion of Silicone Elastomers for Space Applications

    Science.gov (United States)

    de Groh, Henry C.; Puleo, Bernadette J.; Steinetz, Bruce M.

    An investigation of silicone elastomers for seals used in docking and habitat systems for future space exploration vehicles is being conducted at NASA. For certain missions, NASA is considering androgynous docking systems where two vehicles each having a seal would be required to: dock for a period of time, seal effectively, and then separate with minimum push-off forces for undocking. Silicone materials are generally chosen for their wide operating temperatures and low leakage rates. However silicone materials are often sticky and usually exhibit considerable adhesion when mated against metals and silicone surfaces. This paper investigates the adhesion unit pressure for a space rated silicone material (S0383-70) for either seal-on-seal (SoS) or seal-on-aluminum (SoAl) operation modes in the following conditions: as-received, after ground-based atomic-oxygen (AO) pre-treatment, after application of a thin coating of a space-qualified grease (Braycote 601EF), and after a combination of AO pre-treatment and grease coating. In order of descending adhesion reduction, the AO treatment reduced seal adhesion the most, followed by the AO plus grease pre-treatment, followed by the grease treatment. The effects of various treatments on silicone (S0383-70 and ELA-SA-401) outgassing properties were also investigated. The leading adhesion AO pre-treatment reduction led to a slight decrease in outgassing for the S0383-70 material and virtually no change in ELA-SA-401 outgassing.

  2. The role of the achiral template in enantioselective transformations. Radical conjugate additions to alpha-methacrylates followed by hydrogen atom transfer.

    Science.gov (United States)

    Sibi, Mukund P; Sausker, Justin B

    2002-02-13

    We have evaluated various achiral templates (1a-g, 10, and 16) in conjunction with chiral Lewis acids in the conjugate addition of nucleophilic radicals to alpha-methacrylates followed by enantioselective H-atom transfer. Of these, a novel naphthosultam template (10) gave high enantioselectivity in the H-atom-transfer reactions with ee's up to 90%. A chiral Lewis acid derived from MgBr(2) and bisoxazoline (2) gave the highest selectivity in the enantioselective hydrogen-atom-transfer reactions. Non-C(2) symmetric oxazolines (20-25) have also been examined as ligands, and of these, compound 25 gave optimal results (87% yield and 80% ee). Insights into rotamer control in alpha-substituted acrylates and the critical role of the tetrahedral sulfone moiety in realizing high selectivity are discussed.

  3. Determination of diffusion coefficients of oxygen atoms in ZrO2 using first-principles calculations

    International Nuclear Information System (INIS)

    Segi, Takashi; Okuda, Takanari

    2014-01-01

    Density functional theory and nudged elastic band calculations were performed in order to determine the diffusion coefficient for oxygen from monoclinic ZrO 2 . The calculated values for monoclinic ZrO 2 at 1000 K and 1500 K were 5.88 × 10 -16 cm 2 s -1 and 2.91 × 10 -11 cm 2 s -1 , respectively, and agreed with previously determined experimental values. In addition, the results of the nudged elastic band calculations suggest that interstitial oxygen sites exist between stable oxygen sites, and if oxygen atoms occupy these sites, stable structures with values for the lattice angle β of greater than 80.53° may be obtained. (author)

  4. Photolysis of CH3CHO at 248 nm: Evidence of triple fragmentation from primary quantum yield of CH3 and HCO radicals and H atoms

    Science.gov (United States)

    Morajkar, Pranay; Bossolasco, Adriana; Schoemaecker, Coralie; Fittschen, Christa

    2014-06-01

    Radical quantum yields have been measured following the 248 nm photolysis of acetaldehyde, CH3CHO. HCO radical and H atom yields have been quantified by time resolved continuous wave Cavity Ring Down Spectroscopy in the near infrared following their conversion to HO2 radicals by reaction with O2. The CH3 radical yield has been determined using the same technique following their conversion into CH3O2. Absolute yields have been deduced for HCO radicals and H atoms through fitting of time resolved HO2 profiles, obtained under various O2 concentrations, to a complex model, while the CH3 yield has been determined relative to the CH3 yield from 248 nm photolysis of CH3I. Time resolved HO2 profiles under very low O2 concentrations suggest that another unknown HO2 forming reaction path exists in this reaction system besides the conversion of HCO radicals and H atoms by reaction with O2. HO2 profiles can be well reproduced under a large range of experimental conditions with the following quantum yields: CH3CHO + hν248nm → CH3CHO*, CH3CHO* → CH3 + HCO ϕ1a = 0.125 ± 0.03, CH3CHO* → CH3 + H + CO ϕ1e = 0.205 ± 0.04, CH3CHO*{to 2pc{rArrfill}}limits^{o2}CH3CO + HO2 ϕ1f = 0.07 ± 0.01. The CH3O2 quantum yield has been determined in separate experiments as φ_{CH3} = 0.33 ± 0.03 and is in excellent agreement with the CH3 yields derived from the HO2 measurements considering that the triple fragmentation (R1e) is an important reaction path in the 248 nm photolysis of CH3CHO. From arithmetic considerations taking into account the HO2 and CH3 measurements we deduce a remaining quantum yield for the molecular pathway: CH3CHO* → CH4 + CO ϕ1b = 0.6. All experiments can be consistently explained with absence of the formerly considered pathway: CH3CHO* → CH3CO + H ϕ1c = 0.

  5. Photolysis of CH₃CHO at 248 nm: evidence of triple fragmentation from primary quantum yield of CH₃ and HCO radicals and H atoms.

    Science.gov (United States)

    Morajkar, Pranay; Bossolasco, Adriana; Schoemaecker, Coralie; Fittschen, Christa

    2014-06-07

    Radical quantum yields have been measured following the 248 nm photolysis of acetaldehyde, CH3CHO. HCO radical and H atom yields have been quantified by time resolved continuous wave Cavity Ring Down Spectroscopy in the near infrared following their conversion to HO2 radicals by reaction with O2. The CH3 radical yield has been determined using the same technique following their conversion into CH3O2. Absolute yields have been deduced for HCO radicals and H atoms through fitting of time resolved HO2 profiles, obtained under various O2 concentrations, to a complex model, while the CH3 yield has been determined relative to the CH3 yield from 248 nm photolysis of CH3I. Time resolved HO2 profiles under very low O2 concentrations suggest that another unknown HO2 forming reaction path exists in this reaction system besides the conversion of HCO radicals and H atoms by reaction with O2. HO2 profiles can be well reproduced under a large range of experimental conditions with the following quantum yields: CH3CHO + hν(248nm) → CH3CHO*, CH3CHO* → CH3 + HCO ϕ(1a) = 0.125 ± 0.03, CH3CHO* → CH3 + H + CO ϕ(1e) = 0.205 ± 0.04, CH3CHO*[Formula: see text]CH3CO + HO2 ϕ(1f) = 0.07 ± 0.01. The CH3O2 quantum yield has been determined in separate experiments as ϕ(CH₃) = 0.33 ± 0.03 and is in excellent agreement with the CH3 yields derived from the HO2 measurements considering that the triple fragmentation (R1e) is an important reaction path in the 248 nm photolysis of CH3CHO. From arithmetic considerations taking into account the HO2 and CH3 measurements we deduce a remaining quantum yield for the molecular pathway: CH3CHO* → CH4 + CO ϕ(1b) = 0.6. All experiments can be consistently explained with absence of the formerly considered pathway: CH3CHO* → CH3CO + H ϕ(1c) = 0.

  6. Aminoxyl (nitroxyl) radicals in the early decomposition of the nitramine RDX.

    Science.gov (United States)

    Irikura, Karl K

    2013-03-14

    The explosive nitramine RDX (1,3,5-trinitrohexahydro-s-triazine) is thought to decompose largely by homolytic N-N bond cleavage, among other possible initiation reactions. Density-functional theory (DFT) calculations indicate that the resulting secondary aminyl (R2N·) radical can abstract an oxygen atom from NO2 or from a neighboring nitramine molecule, producing an aminoxyl (R2NO·) radical. Persistent aminoxyl radicals have been detected in electron-spin resonance (ESR) experiments and are consistent with autocatalytic "red oils" reported in the experimental literature. When the O-atom donor is a nitramine, a nitrosamine is formed along with the aminoxyl radical. Reactions of aminoxyl radicals can lead readily to the "oxy-s-triazine" product (as the s-triazine N-oxide) observed mass-spectrometrically by Behrens and co-workers. In addition to forming aminoxyl radicals, the initial aminyl radical can catalyze loss of HONO from RDX.

  7. Launch Vehicle Performance for Bipropellant Propulsion Using Atomic Propellants With Oxygen

    Science.gov (United States)

    Palaszewski, Bryan

    2000-01-01

    Atomic propellants for bipropellant launch vehicles using atomic boron, carbon, and hydrogen were analyzed. The gross liftoff weights (GLOW) and dry masses of the vehicles were estimated, and the 'best' design points for atomic propellants were identified. Engine performance was estimated for a wide range of oxidizer to fuel (O/F) ratios, atom loadings in the solid hydrogen particles, and amounts of helium carrier fluid. Rocket vehicle GLOW was minimized by operating at an O/F ratio of 1.0 to 3.0 for the atomic boron and carbon cases. For the atomic hydrogen cases, a minimum GLOW occurred when using the fuel as a monopropellant (O/F = 0.0). The atomic vehicle dry masses are also presented, and these data exhibit minimum values at the same or similar O/F ratios as those for the vehicle GLOW. A technology assessment of atomic propellants has shown that atomic boron and carbon rocket analyses are considered to be much more near term options than the atomic hydrogen rockets. The technology for storing atomic boron and carbon has shown significant progress, while atomic hydrogen is not able to be stored at the high densities needed for effective propulsion. The GLOW and dry mass data can be used to estimate the cost of future vehicles and their atomic propellant production facilities. The lower the propellant's mass, the lower the overall investment for the specially manufactured atomic propellants.

  8. Influence of oxygen impurity atoms on defect clusters and radiation hardening in neutron-irradiated vanadium

    International Nuclear Information System (INIS)

    Bajaj, R.; Wechsler, M.S.

    1975-01-01

    Single crystal TEM samples and polycrystalline tensile samples of vanadium containing 60-640 wt ppm oxygen were irradiated at about 100 0 C to about 1.3 x 10 19 neutrons/cm 2 (E greater than 1 MeV) and post-irradiation annealed up to 800 0 C. The defect cluster density increased and the average size decreased with increasing oxygen concentration. Higher oxygen concentrations caused the radiation hardening and radiation-anneal hardening to increase. The observations are consistent with the nucleation of defect clusters by small oxygen or oxygen-point defect complexes and the trapping of oxygen at defect clusters upon post-irradiation annealing

  9. OH radicals from the indirect actions of X-rays induce cell lethality and mediate the majority of the oxygen enhancement effect.

    Science.gov (United States)

    Hirayama, Ryoichi; Ito, Atsushi; Noguchi, Miho; Matsumoto, Yoshitaka; Uzawa, Akiko; Kobashi, Gen; Okayasu, Ryuichi; Furusawa, Yoshiya

    2013-11-01

    We examined OH radical-mediated indirect actions from X irradiation on cell killing in wild-type Chinese hamster ovary cell lines (CHO and AA8) under oxic and hypoxic conditions, and compared the contribution of direct and indirect actions under both conditions. The contribution of indirect action on cell killing can be estimated from the maximum degree of protection by dimethylsulfoxide, which suppresses indirect action by quenching OH radicals without affecting the direct action of X rays on cell killing. The contributions of indirect action on cell killing of CHO cells were 76% and 50% under oxic and hypoxic conditions, respectively, and those for AA8 cells were 85% and 47%, respectively. Therefore, the indirect action on cell killing was enhanced by oxygen during X irradiation in both cell lines tested. Oxygen enhancement ratios (OERs) at the 10% survival level (D10 or LD90) for CHO and AA8 cells were 2.68 ± 0.15 and 2.76 ± 0.08, respectively. OERs were evaluated separately for indirect and direct actions, which gave the values of 3.75 and 2.01 for CHO, and 4.11 and 1.32 for AA8 cells, respectively. Thus the generally accepted OER value of ∼3 is best understood as the average of the OER values for both indirect and direct actions. These results imply that both indirect and direct actions on cell killing require oxygen for the majority of lethal DNA damage, however, oxygen plays a larger role in indirect than for direct effects. Conversely, the lethal damage induced by the direct action of X rays are less affected by oxygen concentration.

  10. O-, N-Atoms-Coordinated Mn Cofactors within a Graphene Framework as Bioinspired Oxygen Reduction Reaction Electrocatalysts.

    Science.gov (United States)

    Yang, Yang; Mao, Kaitian; Gao, Shiqi; Huang, Hao; Xia, Guoliang; Lin, Zhiyu; Jiang, Peng; Wang, Changlai; Wang, Hui; Chen, Qianwang

    2018-05-28

    Manganese (Mn) is generally regarded as not being sufficiently active for the oxygen reduction reaction (ORR) compared to other transition metals such as Fe and Co. However, in biology, manganese-containing enzymes can catalyze oxygen-evolving reactions efficiently with a relative low onset potential. Here, atomically dispersed O and N atoms coordinated Mn active sites are incorporated within graphene frameworks to emulate both the structure and function of Mn cofactors in heme-copper oxidases superfamily. Unlike previous single-metal catalysts with general M-N-C structures, here, it is proved that a coordinated O atom can also play a significant role in tuning the intrinsic catalytic activities of transition metals. The biomimetic electrocatalyst exhibits superior performance for the ORR and zinc-air batteries under alkaline conditions, which is even better than that of commercial Pt/C. The excellent performance can be ascribed to the abundant atomically dispersed Mn cofactors in the graphene frameworks, confirmed by various characterization methods. Theoretical calculations reveal that the intrinsic catalytic activity of metal Mn can be significantly improved via changing local geometry of nearest coordinated O and N atoms. Especially, graphene frameworks containing the Mn-N 3 O 1 cofactor demonstrate the fastest ORR kinetics due to the tuning of the d electronic states to a reasonable state. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Anti-Adhesion Elastomer Seal Coatings for Ultraviolet and Atomic Oxygen Protection

    Science.gov (United States)

    De Groh, Henry C., III; Puleo, Bernadette J.; Waters, Deborah L.; Miller, Sharon K.

    2015-01-01

    Radiation blocking sunscreen coatings have been developed for the protection of elastomer seals used in low-Earth-orbit (LEO). The coatings protect the seals from ultraviolet (UV) radiation and atomic oxygen (AO) damage. The coatings were developed for use on NASA docking seals. Docking seal damage from the UV and AO present in LEO can constrain mission time-line, flight mode options, and increases risk. A low level of adhesion is also required for docking seals so undocking push-off forces can be low. The coatings presented also mitigate this unwanted adhesion. Greases with low collected volatile condensable materials (CVCM) and low total mass loss (TML) were mixed with slippery and/or UV blocking powders to create the protective coatings. Coatings were applied at rates up to 2 milligrams per square centimeter. Coated seals were exposed to AO and UV in the NUV (near-UV) and UV-C wavelength ranges (300 to 400 nanometers and 254 nanometers, respectively). Ground based ashers were used to simulate the AO of space. The Sun's UV energy was mimicked assuming a nose forward flight mode, resulting in an exposure rate of 2.5 megajoules per square meter per day. Exposures between 0 and 147 megajoules per square meter (UV-C) and 245 megajoules per square meter (NUV) were accomplished. The protective coatings were durable, providing protection from UV after a simulated docking and undocking cycle. The level of protection begins to decline at coverage rates less than 0.9 milligrams per square centimeter. The leakage of seals coated with Braycote plus 20 percent Z-cote ZnO sunscreen increased by a factor of 40 after moderate AO exposure; indicating that this coating might not be suitable due to AO intolerance. Seals coated with DC-7-16.4 percent Z-cote ZnO sunscreen were not significantly affected by combined doses of 2 x 10 (sup 21) atoms per square AO with 73 megajoules per square meter UV-C. Unprotected seals were significantly damaged at UV-C exposures of 0.3 megajoules per

  12. Tobacco Smoke: Involvement of Reactive Oxygen Species and Stable Free Radicals in Mechanisms of Oxidative Damage, Carcinogenesis and Synergistic Effects with Other Respirable Particles

    Directory of Open Access Journals (Sweden)

    Konstantinos Fiotakis

    2009-02-01

    Full Text Available Tobacco smoke contains many toxic, carcinogenic and mutagenic chemicals, as well as stable and unstable free radicals and reactive oxygen species (ROS in the particulate and the gas phase with the potential for biological oxidative damage. Epidemiological evidence established that smoking is one of the most important extrinsic factor of premature morbidity and mortality. The objective of this study was to investigate oxidative and carcinogenic mechanisms of tobacco and synergistic action with other respirable particles in the respiratory system of smokers. Electron Paramagnetic Resonance (EPR and spin- trapping techniques were used to study stable free radicals in the cigarette tar, and unstable superoxide anion (O2·- and hydroxyl (HO· radicals in the smoke Results showed that the semiquinone radical system has the potential for redox recycling and oxidative action. Further, results proved that aqueous cigarette tar (ACT solutions can generate adducts with DNA nucleobases, particularly the mutagenic 8-hydroxy-2’-deoxyguanosine (a biomarker for carcinogenesis.Also, we observed synergistic effects in the generation of HO·, through the Fenton reaction, with environmental respirable particles (asbestos fibres, coal dust, etc. and ambient particulate matter (PM, such as PM10, PM2.5 and diesel exhaust particles (DEP. The highest synergistic effects was observed with the asbestos fibres (freshly grounded, PM2.5 and DEP. Finally, we discuss results from our previous study of conventional cellulose acetate filters and “bio-filters” with hemoglobin impregnated activated carbon, which showed that these filters do not substantially alter the free radical content of smoke in the particulate and in the gaseous phase.

  13. Tobacco Smoke: Involvement of Reactive Oxygen Species and Stable Free Radicals in Mechanisms of Oxidative Damage, Carcinogenesis and Synergistic Effects with Other Respirable Particles

    Science.gov (United States)

    Valavanidis, Athanasios; Vlachogianni, Thomais; Fiotakis, Konstantinos

    2009-01-01

    Tobacco smoke contains many toxic, carcinogenic and mutagenic chemicals, as well as stable and unstable free radicals and reactive oxygen species (ROS) in the particulate and the gas phase with the potential for biological oxidative damage. Epidemiological evidence established that smoking is one of the most important extrinsic factor of premature morbidity and mortality. The objective of this study was to investigate oxidative and carcinogenic mechanisms of tobacco and synergistic action with other respirable particles in the respiratory system of smokers. Electron Paramagnetic Resonance (EPR) and spin-trapping techniques were used to study stable free radicals in the cigarette tar, and unstable superoxide anion (O2•−) and hydroxyl (HO•) radicals in the smoke Results showed that the semiquinone radical system has the potential for redox recycling and oxidative action. Further, results proved that aqueous cigarette tar (ACT) solutions can generate adducts with DNA nucleobases, particularly the mutagenic 8-hydroxy-2’-deoxyguanosine (a biomarker for carcinogenesis). Also, we observed synergistic effects in the generation of HO•, through the Fenton reaction, with environmental respirable particles (asbestos fibres, coal dust, etc.) and ambient particulate matter (PM), such as PM10, PM2.5 and diesel exhaust particles (DEP). The highest synergistic effects was observed with the asbestos fibres (freshly grounded), PM2.5 and DEP. Finally, we discuss results from our previous study of conventional cellulose acetate filters and “bio-filters” with hemoglobin impregnated activated carbon, which showed that these filters do not substantially alter the free radical content of smoke in the particulate and in the gaseous phase. PMID:19440393

  14. Involvement of oxygen free radicals in the respiratory uncoupling induced by free calcium and ADP-magnesium in isolated cardiac mitochondria: comparing reoxygenation in cultured cardiomyocytes.

    Science.gov (United States)

    Meynier, Alexandra; Razik, Hafida; Cordelet, Catherine; Grégoire, Stéphane; Demaison, Luc

    2003-01-01

    Recently, we have observed that the simultaneous application of free calcium (fCa) and ADP-magnesium (Mg) reduced the ADP:O ratio in isolated cardiac mitochondria. The uncoupling was prevented by cyclosporin A, an inhibitor of the permeability transition pore. The purpose of this study was to know if the generation of oxygen free radicals (OFR) is involved in this phenomenon and if it occurs during reoxygenation (Reox) of cultured cardiomyocytes. Cardiac mitochondria were harvested from male Wistar rats. Respiration was assessed in two media with different fCa concentrations (0 or 0.6 microM) with palmitoylcarnitine and ADP-Mg as respiration substrates. The production of Krebs cycle intermediates (KCI) was determined. Without fCa in the medium, the mitochondria displayed a large production of citrate + isocitrate + alpha-ketoglutarate. fCa drastically reduced these KCI and promoted the accumulation of succinate. To know if OFR are involved in the respiratory uncoupling, the effect of 4OH-TEMPO (250 microM), a hydrosoluble scavenger of OFR, was tested. 4OH-TEMPO completely abolished the fCa- and ADP-Mg-induced uncoupling. Conversely, vitamin E contributed to further decreasing the ADP:O ratio. Since no hydrosoluble electron acceptor was added in our experiment, the oxygen free radical-induced oxidized vitamin E was confined near the mitochondrial membranes, which should reduce the ADP:O ratio by opening the permeability transition pore. The generation of OFR could result from the matrix accumulation of succinate. Taken together, these results indicate that mitochondrial Ca uptake induces a slight increase in membrane permeability. Thereafter, Mg enters the matrix and, in combination with Ca, stimulates the isocitrate and/or alpha-ketoglutarate dehydrogenases. Matrix succinate favors oxygen free radical generation that further increases membrane permeability and allows respiratory uncoupling through proton leakage. To determine whether the phenomenon takes place

  15. Atoms

    International Nuclear Information System (INIS)

    Fuchs, Alain; Villani, Cedric; Guthleben, Denis; Leduc, Michele; Brenner, Anastasios; Pouthas, Joel; Perrin, Jean

    2014-01-01

    Completed by recent contributions on various topics (atoms and the Brownian motion, the career of Jean Perrin, the evolution of atomic physics since Jean Perrin, relationship between scientific atomism and philosophical atomism), this book is a reprint of a book published at the beginning of the twentieth century in which the author addressed the relationship between atomic theory and chemistry (molecules, atoms, the Avogadro hypothesis, molecule structures, solutes, upper limits of molecular quantities), molecular agitation (molecule velocity, molecule rotation or vibration, molecular free range), the Brownian motion and emulsions (history and general features, statistical equilibrium of emulsions), the laws of the Brownian motion (Einstein's theory, experimental control), fluctuations (the theory of Smoluchowski), light and quanta (black body, extension of quantum theory), the electricity atom, the atom genesis and destruction (transmutations, atom counting)

  16. Atom Transfer Radical Polymerization of Styrene in Presence of Mesoporous Silica Nanoparticles: Application of Reverse, Simultaneous Reverse and Normal Initiation Techniques

    Directory of Open Access Journals (Sweden)

    Khezrollah Khezri

    2014-04-01

    Full Text Available Atom transfer radical polymerization (ATRP of styrene in presence of mesoporous silica nanoparticles was carried out at 110 °C. Reverse atom transfer radical polymerization (RATRP and simultaneous reverse and normal initiation for atom transfer radical polymerization (SR&NI ATRP techniques were used as two appropriate introduced techniques for circumventing oxidation problems. Usage of metal catalyst in its higher oxidation state was the main feature of these initiation techniques in which deficiencies of normal ATRP were circumvented. Structure, surface area and pore diameter of synthesized mesoporous silica nanoparticles were evaluated using X–ray diffraction and nitrogen adsorption/desorption isotherm analysis. Average particle size was estimated around 600 nm by electron microscopy images. In addition, according to these images, nanoparticles revealed an appropriate size distribution. Particles size and their distribution were examined using scanning. Final monomer conversion was determined by using gas chromatography. The number and weight average molecular weights (Mn and Mw and polydispersity indexes (PDI were also evaluated by gel permeation chromatography. According to the results obtained, addition of mesoporous silica nanoparticles in both RATRP and SR&NI ATRP systems revealed similar effects: decrement of conversion and Mn and also increment of PDI values observed by increasing of mesoporous silica nanoparticles content. Improvement in thermal stability of the nanocomposites in comparison with neat polystyrene was demonstrated by thermogravimetric analysis (TGA. Moreover, in case of nanocomposites, thermal stability was obtained by higher loading of nanoparticles. A decrease in glass transition temperature by higher content of mesoporous silica nanoparticles has been demonstrated by differential scanning calorimetry analysis.

  17. High-performance liquid chromatographic method to evaluate the hydrogen atom transfer during reaction between 1,1-diphenyl-2-picryl-hydrazyl radical and antioxidants

    International Nuclear Information System (INIS)

    Boudier, Ariane; Tournebize, Juliana; Bartosz, Grzegorz; El Hani, Safae; Bengueddour, Rachid; Sapin-Minet, Anne; Leroy, Pierre

    2012-01-01

    Highlights: ► Both 1,1-diphenyl-2-picrylhydrazyl radical and its product measurement by HPLC. ► Lowest limit of detection by monitoring 1,1-diphenyl-2-picryl-hydrazine. ► Adsorption problem of the radical on HPLC parts have been pointed out. - Abstract: 1,1-Diphenyl-2-picrylhydrazyl (DPPH·) is a stable nitrogen centred radical widely used to evaluate direct radical scavenging properties of various synthetic or natural antioxidants (AOs). The bleaching rate of DPPH· absorbance at 515 nm is usually monitored for this purpose. In order to avoid the interference of complex coloured natural products used as antioxidant supplements or cosmetics, HPLC systems have been reported as alternative techniques to spectrophotometry. They also rely upon measurement of DPPH· quenching rate and none of them permits to identify and measure 1,1-diphenyl-2-picryl-hydrazine (DPPH-H), the reduced product of DPPH· resulting from hydrogen atom transfer (HAT), which is the main mechanism of the reaction between DPPH· and AOs. We presently report an HPLC method devoted to the simultaneous measurement of DPPH· and DPPH-H. Both were fully separated on a C18 column eluted with acetonitrile–10 mM ammonium citrate buffer pH 6.8 (70:30, v/v) and detected at 330 nm. Adsorption process of DPPH· onto materials of the HPLC system was pointed out. Consequently, the linearity range observed for DPPH· was restricted, thus a much lower limit of detection was obtained for DPPH-H than for DPPH· using standards (0.02 and 14 μM, respectively). The method was applied to three commonly used AOs, i.e. Trolox ® , ascorbic acid and GSH, and compared with spectrophotometry. Further application to complex matrices (cell culture media, vegetal extracts) and nanomaterials demonstrated (i) its usefulness because of higher selectivity than colorimetry, and (ii) its help to investigate the mechanisms occurring with the free radical.

  18. Mechanism of pulse discharge production of iodine atoms from CF3I molecules for a chemical oxygen-iodine laser

    International Nuclear Information System (INIS)

    Kochetov, I V; Napartovich, A P; Vagin, N P; Yuryshev, N N

    2009-01-01

    The pulsed chemical oxygen-iodine laser (COIL) development is aimed at many new applications. Pulsed electric discharge is most effective in turning COIL operation into the pulse mode by instant production of iodine atoms. A numerical model is developed for simulations of the pulsed COIL initiated by an electric discharge. The model comprises a system of kinetic equations for neutral and charged species, electric circuit equation, gas thermal balance equation and the photon balance equation. Reaction rate coefficients for processes involving electrons are found by solving the electron Boltzmann equation, which is re-calculated in a course of computations when plasma parameters changed. The processes accounted for in the Boltzmann equation include excitation and ionization of atoms and molecules, dissociation of molecules, electron attachment processes, electron-ion recombination, electron-electron collisions, second-kind collisions and stepwise excitation of molecules. The last processes are particularly important because of a high singlet oxygen concentration in gas flow from the singlet oxygen chemical generator. Results of numerical simulations are compared with experimental laser pulse waveforms. It is concluded that there is satisfactory agreement between theory and the experiment. The prevailing mechanism of iodine atom formation from the CF 3 I donor in a very complex kinetic system of the COIL medium under pulse discharge conditions, based on their detailed numerical modelling and by comparing these results both with experimental results of other authors and their own experiments, is established. The dominant iodine atom production mechanism for conditions under study is the electron-impact dissociation of CF 3 I molecules. It was proved that in the conditions of the experiment the secondary chemical reactions with O atoms play an insignificant role.

  19. Oxygen-driving and atomized mucosolvan inhalation combined with holistic nursing in the treatment of children severe bronchial pneumonia.

    Science.gov (United States)

    Yang, Fang

    2015-07-01

    This paper aimed to discuss the method, effect and safety of oxygen-driving and atomized Mucosolvan inhalation combined with holistic nursing in the treatment of children severe bronchial pneumonia. Totally 90 children with severe bronchial pneumonia who were treated in our hospital from March 2013 to November 2013 were selected as the research objects. Based on randomized controlled principle, those children were divided into control group, test group I and test group II according to the time to enter the hospital, 30 in each group. Patients in control group was given conventional therapy; test group I was given holistic nursing combined with conventional therapy; test group II was given oxygen-driving and atomized Mucosolvan inhalation combined with holistic nursing on the basis of conventional therapy. After test, the difference of main symptoms in control group, test group I and II was of no statistical significance (P>0.05). Test group II was found with the best curative effect, secondary was test group I and control group was the last. It can be concluded that, oxygen-driving and atomized Mucosolvan inhalation combined with holistic nursing has certain effect in the treatment of children severe bronchial pneumonia and is better than holistic nursing only.

  20. Oxygen-atom transfer chemistry and thermolytic properties of a di-tert-butylphosphate-ligated Mn4O4 cubane.

    Science.gov (United States)

    Van Allsburg, Kurt M; Anzenberg, Eitan; Drisdell, Walter S; Yano, Junko; Tilley, T Don

    2015-03-16

    [Mn4O4{O2P(OtBu)2}6] (1), an Mn4O4 cubane complex combining the structural inspiration of the photosystem II oxygen-evolving complex with thermolytic precursor ligands, was synthesized and fully characterized. Core oxygen atoms within complex 1 are transferred upon reaction with an oxygen-atom acceptor (PEt3), to give the butterfly complex [Mn4O2{O2P(OtBu)2}6(OPEt3)2]. The cubane structure is restored by reaction of the latter complex with the O-atom donor PhIO. Complex 1 was investigated as a precursor to inorganic Mn metaphosphate/pyrophosphate materials, which were studied by X-ray absorption spectroscopy to determine the fate of the Mn4O4 unit. Under the conditions employed, thermolyses of 1 result in reduction of the manganese to Mn(II) species. Finally, the related butterfly complex [Mn4O2{O2P(pin)}6(bpy)2] (pin = pinacolate) is described. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Synthesis of Well-Defined Three-Arm Star-Branched Polystyrene through Arm-First Coupling Approach by Atom Transfer Radical Polymerization

    Directory of Open Access Journals (Sweden)

    Syed Shahabuddin

    2015-01-01

    Full Text Available Here we describe a simple route to synthesize three-arm star-branched polystyrene. Atom transfer radical polymerization technique has been utilized to yield branched polystyrene involving Williamson coupling strategy. Initially a linear polymeric chain of predetermined molecular weight has been synthesized which is further end-functionalized into a primary alkyl bromide moiety, a prime requisition for Williamson reaction. The end-functionalized polymer is then coupled using 1,1,1-tris(4-hydroxyphenylethane, a trifunctional core molecule, to give well-defined triple-arm star-branched polystyrene.

  2. Controlled Grafting of Poly(methyl methacrylate) Brushes on Poly(vinylidene fluoride) Powders by Surface-initiated Atom Transfer Radical Polymerization

    Institute of Scientific and Technical Information of China (English)

    TANG Zhaoqi; LI Wei; LIU Lanqin; HUANG Lei; ZHOU Jin; YU Haiyin

    2009-01-01

    Controlled grafting of well-defined polymer brushes of methyl methacrylate (MMA) on the poly(vinylidene fluoride) (PVDF) powders was carded out by the surface-initiated atom transfer radical polymerization (ATRP). The ATRP initiator was anchored on the PVDF surface by alkaline treatment, followed by UV-induced bromination; then methyl methacrylate (MMA) was grafted onto the brominated PVDF by the ATRP technique. The chemical composition changes of PVDF were characterized by Fourier transform-infrared spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS). FT-IR and XPS results clearly indicated the successful graft of poly(methyl methacrylate) onto the PVDF surface.

  3. Ab initio R1 mechanism of photostimulated oxygen isotope exchange reaction on a defect TiO{sub 2} surface: The case of terminal oxygen atom exchange

    Energy Technology Data Exchange (ETDEWEB)

    Kevorkyants, Ruslan, E-mail: ruslan.kevorkyants@gmail.com; Sboev, Mikhail N.; Chizhov, Yuri V.

    2017-05-01

    Highlights: • DFT R1 mechanism of photostimulated oxygen isotope exchange between {sup 16}O{sup 18}O and terminal oxygen atom of a defect surface of nanocrystalline TiO{sub 2} is proposed. • The mechanism involves four adsorption intermediates and five transition states. • Activation energy of the reaction is 0.24 eV. • G-tensors of O{sub 3}{sup −} intermediates match EPR data on O{sub 2} adsorbed on UV-irradiated TiO{sub 2} surface. - Abstract: Based on density functional theory we propose R1 mechanism of photostimulated oxygen isotope exchange (POIEx) reaction between {sup 16}O{sup 18}O and terminal oxygen atom of a defect TiO{sub 2} surface, which is modeled by amorphous Ti{sub 8}O{sub 16} nanocluster in excited S{sup 1} electronic state. The proposed mechanism involves four adsorption intermediates and five transition states. The computed activation energy of the POIEx equals 0.24 eV. The computed g-tensors of the predicted ozonide O{sub 3}{sup −} chemisorption species match well EPR data on O{sub 2} adsorption on UV-irradiated nanocrystalline TiO{sub 2}. This match serves a mean of justification of the proposed R1 mechanism of the POIEx reaction. In addition, it is found that the proposed R1 POIEx reaction’s mechanism differs from R1 mechanism of thermo-assisted OIEx reaction on a surface of supported vanadium oxide catalyst VO{sub x}/TiO{sub 2} reported earlier.

  4. N,2,3,4-Tetrasubstituted Pyrrolidines through Tandem Lithium Amide Conjugate Addition/Radical Cyclization/Oxygenation Reactions

    Czech Academy of Sciences Publication Activity Database

    Kafka, František; Pohl, Radek; Císařová, I.; Mackman, R.; Bahador, G.; Jahn, Ullrich

    2016-01-01

    Roč. 2016, č. 22 (2016), s. 3862-3871 ISSN 1434-193X R&D Projects: GA ČR GA13-40188S Grant - others:COST(XE) CM1201 Institutional support: RVO:61388963 Keywords : tandem reactions * nitrogen heterocycles * Michael addition * radical reactions * cyclization * enolates Subject RIV: CC - Organic Chemistry Impact factor: 2.834, year: 2016

  5. Role of N2 molecules in pulse discharge production of I atoms for a pulsed chemical oxygen-iodine laser

    International Nuclear Information System (INIS)

    Kochetov, I V; Napartovich, A P; Vagin, N P; Yuryshev, N N

    2011-01-01

    A pulsed electric discharge is the most effective means to turn chemical oxygen-iodine laser (COIL) operation into the pulse mode by fast production of iodine atoms. Experimental studies and numerical simulations are performed on a pulsed COIL initiated by an electric discharge in a mixture CF 3 I : N 2 : O 2 ( 3 X) : O 2 (a 1 Δ g ) flowing out of a chemical singlet oxygen generator. A transverse pulsed discharge is realized at various iodide pressures. The model comprises a system of kinetic equations for neutral and charged species, the electric circuit equation, the gas thermal balance equation and the photon balance equation. Reaction rate coefficients for processes involving electrons are repeatedly re-calculated by the electron Boltzmann equation solver when the plasma parameters are changed. The processes accounted for in the Boltzmann equation include direct and stepwise excitation and ionization of atoms and molecules, dissociation of molecules, electron attachment processes, electron-ion recombination, electron-electron collisions and second-kind collisions. The last processes are particularly important because of a high singlet oxygen concentration in gas flow from the singlet oxygen chemical generator. A conclusion is drawn about satisfactory agreement between the theory and the experiment.

  6. Synthesis of defined polyhedral oligosilsesquioxane-containing diblock and triblock methacrylate copolymers by atom transfer radical polymerization

    Czech Academy of Sciences Publication Activity Database

    Janata, Miroslav; Sikora, Antonín; Látalová, Petra; Čadová, Eva; Raus, Vladimír; Matějka, Libor; Vlček, Petr

    2013-01-01

    Roč. 128, č. 6 (2013), s. 4294-4301 ISSN 0021-8995 R&D Projects: GA ČR GAP106/12/0844; GA ČR GAP108/12/1459 Institutional support: RVO:61389013 Keywords : copolymers * nanostructured polymers * radical polymerization Subject RIV: CD - Macromolecular Chemistry Impact factor: 1.640, year: 2013

  7. Ultrafast atomic layer-by-layer oxygen vacancy-exchange diffusion in double-perovskite LnBaCo2O5.5+δ thin films.

    Science.gov (United States)

    Bao, Shanyong; Ma, Chunrui; Chen, Garry; Xu, Xing; Enriquez, Erik; Chen, Chonglin; Zhang, Yamei; Bettis, Jerry L; Whangbo, Myung-Hwan; Dong, Chuang; Zhang, Qingyu

    2014-04-22

    Surface exchange and oxygen vacancy diffusion dynamics were studied in double-perovskites LnBaCo2O5.5+δ (LnBCO) single-crystalline thin films (Ln = Er, Pr; -0.5 atoms in the LnBCO thin films is taking the layer by layer oxygen-vacancy-exchange mechanism. The first principles density functional theory calculations indicate that hydrogen atoms are present in LnBCO as bound to oxygen forming O-H bonds. This unprecedented oscillation phenomenon provides the first direct experimental evidence of the layer by layer oxygen vacancy exchange diffusion mechanism.

  8. Oxygen atom transfer from a trans-dioxoruthenium(VI) complex to nitric oxide.

    Science.gov (United States)

    Man, Wai-Lun; Lam, William W Y; Ng, Siu-Mui; Tsang, Wenny Y K; Lau, Tai-Chu

    2012-01-02

    In aqueous acidic solutions trans-[Ru(VI)(L)(O)(2)](2+) (L=1,12-dimethyl-3,4:9,10-dibenzo-1,12-diaza-5,8-dioxacyclopentadecane) is rapidly reduced by excess NO to give trans-[Ru(L)(NO)(OH)](2+). When ≤1 mol equiv NO is used, the intermediate Ru(IV) species, trans-[Ru(IV)(L)(O)(OH(2))](2+), can be detected. The reaction of [Ru(VI)(L)(O)(2)](2+) with NO is first order with respect to [Ru(VI)] and [NO], k(2)=(4.13±0.21)×10(1) M(-1) s(-1) at 298.0 K. ΔH(≠) and ΔS(≠) are (12.0±0.3) kcal mol(-1) and -(11±1) cal mol(-1) K(-1), respectively. In CH(3)CN, ΔH(≠) and ΔS(≠) have the same values as in H(2)O; this suggests that the mechanism is the same in both solvents. In CH(3)CN, the reaction of [Ru(VI)(L)(O)(2)](2+) with NO produces a blue-green species with λ(max) at approximately 650 nm, which is characteristic of N(2)O(3). N(2)O(3) is formed by coupling of NO(2) with excess NO; it is relatively stable in CH(3)CN, but undergoes rapid hydrolysis in H(2)O. A mechanism that involves oxygen atom transfer from [Ru(VI)(L)(O)(2)](2+) to NO to produce NO(2) is proposed. The kinetics of the reaction of [Ru(IV)(L)(O)(OH(2))](2+) with NO has also been investigated. In this case, the data are consistent with initial one-electron O(-) transfer from Ru(IV) to NO to produce the nitrito species [Ru(III)(L)(ONO)(OH(2))](2+) (k(2)>10(6) M(-1) s(-1)), followed by a reaction with another molecule of NO to give [Ru(L)(NO)(OH)](2+) and NO(2)(-) (k(2)=54.7 M(-1) s(-1)). Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Statistical analysis of thermospheric gravity waves from Fabry-Perot Interferometer measurements of atomic oxygen

    Directory of Open Access Journals (Sweden)

    E. A. K. Ford

    2008-02-01

    Full Text Available Data from the Fabry-Perot Interferometers at KEOPS (Sweden, Sodankylä (Finland, and Svalbard (Norway, have been analysed for gravity wave activity on all the clear nights from 2000 to 2006. A total of 249 nights were available from KEOPS, 133 from Sodankylä and 185 from the Svalbard FPI. A Lomb-Scargle analysis was performed on each of these nights to identify the periods of any wave activity during the night. Comparisons between many nights of data allow the general characteristics of the waves that are present in the high latitude upper thermosphere to be determined. Comparisons were made between the different parameters: the atomic oxygen intensities, the thermospheric winds and temperatures, and for each parameter the distribution of frequencies of the waves was determined. No dependence on the number of waves on geomagnetic activity levels, or position in the solar cycle, was found. All the FPIs have had different detectors at various times, producing different time resolutions of the data, so comparisons between the different years, and between data from different sites, showed how the time resolution determines which waves are observed. In addition to the cutoff due to the Nyquist frequency, poor resolution observations significantly reduce the number of short-period waves (<1 h period that may be detected with confidence. The length of the dataset, which is usually determined by the length of the night, was the main factor influencing the number of long period waves (>5 h detected. Comparisons between the number of gravity waves detected at KEOPS and Sodankylä over all the seasons showed a similar proportion of waves to the number of nights used for both sites, as expected since the two sites are at similar latitudes and therefore locations with respect to the auroral oval, confirming this as a likely source region. Svalbard showed fewer waves with short periods than KEOPS data for a season when both had the same time resolution data

  10. Accurate Cross Sections for Excitation of Resonance Transitions in Atomic Oxygen

    Science.gov (United States)

    Tayal, S. S.

    2004-01-01

    Electron collision excitation cross sections for the resonance 2p(sup)4 (sup 3)P-2p(sup 3)3s (sup 3)S(sup 0), 2p(sup 4) (sup 3)P-2p(sup 3)3d (sup 3)D(sup 0), 2p4 (sup 3)P-2p(sup 3)3s (sup 3)D(sup 0), 2p(sup 4) (sup 3)P-2p(sup 3)3s (sup 3)P(sup 0) and 2p(sup 4) (sup 3)P-2s2p(sup 5) (sup 3)P(sup 0) transitions have been calculated by using the R matrix with a pseudostates approach for incident electron energies from near threshold to 100 eV. The excitation of these transition sgives rise to strong atomic oxygen emission features at 1304, 1027, 989, 878, and 792 Angstrom in the spectra of several planetary atmospheres. We included 22 spectroscopic bound and autoionizing states and 30 pseudostates in the close-coupling expansion. The target wave functions are chosen to properly account for the important correlation and relaxation effects. The effect of coupling to the continuum is included through the use of pseudostates. The contribution of the ionization continuum is significant for resonance transitions. Measured absolute direct excitation cross sections of 0 I are reported by experimental groups from the Jet Propulsion Laboratory and Johns Hopkins University. Good agreement is noted for the 2p(sup)4 (sup 3)P-2p(sup 3)3s (sup 3)S(sup 0) transition (lambda 1304 Ang) with measured cross sections from both groups that agree well with each other. There is disagreement between experiments for other transitions. Our results support the measured cross sections from the Johns Hopkins University for the 2p(sup 4) (sup 3)P-2p(sup 3)3d (sup 3)D(sup 0) and 2p4 (sup 3)P-2p(sup 3)3s (sup 3)D(sup 0) transitions, while for the 2p4 (sup 3)P-2p(sup 3)3s (sup 3)D(sup 0) transition the agreement is switched to the measured cross sections from the Jet Propulsion Laboratory.

  11. Reactions of carbon radicals generated by 1,5-transposition of reactive centers

    Directory of Open Access Journals (Sweden)

    ZIVORAD CEKOVIC

    2005-03-01

    Full Text Available Radical intermediates can undergo specific reactions, such as intramolecular rearrangements, i.e., the transpositions of radical centers, which are not known in classical ionic organic reactions. 1,5-Transposition of a radical center to a non-activated carbon atom are of great synthetic importance. It can be successfully applied for the introduction of different functional groups (oxygen, nitrogen, sulfur, halogens onto a carbon atom remote from the present functional group. In addition to functionalization of a remote non-activated carbon atom, the formation of new C-C bonds on the d-carbon atom have also been achieved. 1,5-Transposition of the radical centers takes place from alkoxyl, aminyl and carbon radicals to a remote carbon atom. Relocation of the radical centers preferentially involves 1,5-transfer of a hydrogen atom, although migrations of some other groups are known. The reactions of the carbon radical generated by 1,5-relocation of the radical center are presented and their synthetic applications are reviewed.

  12. Radicais livres de oxigênio: um software introdutório Oxygen free radicals: an introductory software

    Directory of Open Access Journals (Sweden)

    Daniela K. Yokaichiya

    2000-04-01

    Full Text Available Though Free Radicals is one of the most frequently explored scientific subjects in mass communication media, the topic is absent of many Biochemistry introductory courses, especially those in which the students do not have a good chemical background. To overcome this contradictory situation we have developed a software treating this topic in a very simple way. The software is divided in four sections: (1 definition and description of free radicals, (2 production pathways, (3 mechanism of action and (4 enzymatic and non enzymatic protection. The instructional capacity of the software has been both qualitative and quantitatively evaluated through its application in undergraduate courses. The software is available in the INTERNET at the site: http://www.unicamp.br/ib/bioquimica/ensino.

  13. Surface modification of thermoplastic poly(vinyl alcohol)/saponite nanocomposites via surface-initiated atom transfer radical polymerization enhanced by air dielectric discharges barrier plasma treatment

    International Nuclear Information System (INIS)

    Zhen Weijun; Lu Canhui

    2012-01-01

    To improve the water resistance of thermoplastic poly(vinyl alcohol)/saponite nanocomposites (TPVA), a simple two-step method was developed for the covalent immobilization of atom transfer radical polymerization (ATRP) initiators on the TPVA surfaces enhanced by air dielectric barrier discharges (DBD) plasma treatment, and hydrophobic poly(methyl methacrylate) (PMMA) brushes were then grafted onto the surface of TPVA via surface-initiated atom transfer radical polymerization (SI-ATRP). The chemical composition, morphology and hydrophobicity of the modified TPVA surfaces were characterized by X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM), respectively. The water resistance of the surface-functionalized PMMA was evaluated by the contact angle and water adsorption method. It was shown that air DBD plasma treatment activated the TPVA surface and accelerated the immobilization of ATRP initiator on the TPVA surface. Compared with TPVA control, TPVA modified by SI-ATRP can be grafted well-defined and covalently tethered network PMMA brushes onto the surface and the hydrophobicity of TPVA were significantly enhanced.

  14. Fluorescence measurement of atomic oxygen concentration in a dielectric barrier discharge

    Czech Academy of Sciences Publication Activity Database

    Dvořák, P.; Mrkvičková, M.; Obrusník, A.; Kratzer, Jan; Dědina, Jiří; Procházka, V.

    2017-01-01

    Roč. 26, č. 6 (2017), s. 1-11, č. článku 065020. ISSN 0963-0252 R&D Projects: GA ČR GA14-23532S; GA ČR(CZ) GA17-04329S Institutional support: RVO:68081715 Keywords : TALIF * dielectric barrier discharge * O radicals Impact factor: 3.302, year: 2016

  15. Adsorption Energies of Carbon, Nitrogen, and Oxygen Atoms on the Low-temperature Amorphous Water Ice: A Systematic Estimation from Quantum Chemistry Calculations

    Science.gov (United States)

    Shimonishi, Takashi; Nakatani, Naoki; Furuya, Kenji; Hama, Tetsuya

    2018-03-01

    We propose a new simple computational model to estimate the adsorption energies of atoms and molecules to low-temperature amorphous water ice, and we present the adsorption energies of carbon (3 P), nitrogen (4 S), and oxygen (3 P) atoms based on quantum chemistry calculations. The adsorption energies were estimated to be 14,100 ± 420 K for carbon, 400 ± 30 K for nitrogen, and 1440 ± 160 K for oxygen. The adsorption energy of oxygen is consistent with experimentally reported values. We found that the binding of a nitrogen atom is purely physisorption, while that of a carbon atom is chemisorption, in which a chemical bond to an O atom of a water molecule is formed. That of an oxygen atom has a dual character, with both physisorption and chemisorption. The chemisorption of atomic carbon also implies the possibility of further chemical reactions to produce molecules bearing a C–O bond, though this may hinder the formation of methane on water ice via sequential hydrogenation of carbon atoms. These properties would have a large impact on the chemical evolution of carbon species in interstellar environments. We also investigated the effects of newly calculated adsorption energies on the chemical compositions of cold dense molecular clouds with the aid of gas-ice astrochemical simulations. We found that abundances of major nitrogen-bearing molecules, such as N2 and NH3, are significantly altered by applying the calculated adsorption energy, because nitrogen atoms can thermally diffuse on surfaces, even at 10 K.

  16. Hydroxyl-radical-induced oxidation of cyclic dipeptides: Reactions of free peptide radicals and their peroxyl radicals

    International Nuclear Information System (INIS)

    Mieden, O.J.

    1989-01-01

    In the course of this study investigations were carried out into the reactions of hydroxyl radicals and hydrogen atoms with cyclic dipeptides as well as the subsequent reactions of peptide radicals and their peroxyl radicals in aqueous solution. The radiolysis products formed in the absence and presence of oxygen or transient metal complexes were characterized and determined on a quantitative basis. The linking of information from product analyses to the kinetic data for transient species obtained by time-resolving UV/VIS and conductivity measurements (pulse radiolysis) as well as computer-assisted simulations of individual events during the reaction permitted an evaluation of the mechanisms underlying the various processes and an identification of interim products with short life-times, which did or did not belong to the group of radicals. Through the characterization of key reactions of radicals and peroxyl radicals of this substance class a major advance has been made towards a better understanding of the role of radicals in the peptide compound and the mechanisms involved in indirect radiation effects on long-chain peptides and proteins. (orig.) [de

  17. Surface recombination of oxygen atoms in O2 plasma at increased pressure: II. Vibrational temperature and surface production of ozone

    Science.gov (United States)

    Lopaev, D. V.; Malykhin, E. M.; Zyryanov, S. M.

    2011-01-01

    Ozone production in an oxygen glow discharge in a quartz tube was studied in the pressure range of 10-50 Torr. The O3 density distribution along the tube diameter was measured by UV absorption spectroscopy, and ozone vibrational temperature TV was found comparing the calculated ab initio absorption spectra with the experimental ones. It has been shown that the O3 production mainly occurs on a tube surface whereas ozone is lost in the tube centre where in contrast the electron and oxygen atom densities are maximal. Two models were used to analyse the obtained results. The first one is a kinetic 1D model for the processes occurring near the tube walls with the participation of the main particles: O(3P), O2, O2(1Δg) and O3 molecules in different vibrational states. The agreement of O3 and O(3P) density profiles and TV calculated in the model with observed ones was reached by varying the single model parameter—ozone production probability (\\gamma_{O_{3}}) on the quartz tube surface on the assumption that O3 production occurs mainly in the surface recombination of physisorbed O(3P) and O2. The phenomenological model of the surface processes with the participation of oxygen atoms and molecules including singlet oxygen molecules was also considered to analyse \\gamma_{O_{3}} data obtained in the kinetic model. A good agreement between the experimental data and the data of both models—the kinetic 1D model and the phenomenological surface model—was obtained in the full range of the studied conditions that allowed consideration of the ozone surface production mechanism in more detail. The important role of singlet oxygen in ozone surface production was shown. The O3 surface production rate directly depends on the density of physisorbed oxygen atoms and molecules and can be high with increasing pressure and energy inputted into plasma while simultaneously keeping the surface temperature low enough. Using the special discharge cell design, such an approach opens up the

  18. Surface recombination of oxygen atoms in O2 plasma at increased pressure: II. Vibrational temperature and surface production of ozone

    International Nuclear Information System (INIS)

    Lopaev, D V; Malykhin, E M; Zyryanov, S M

    2011-01-01

    Ozone production in an oxygen glow discharge in a quartz tube was studied in the pressure range of 10-50 Torr. The O 3 density distribution along the tube diameter was measured by UV absorption spectroscopy, and ozone vibrational temperature T V was found comparing the calculated ab initio absorption spectra with the experimental ones. It has been shown that the O 3 production mainly occurs on a tube surface whereas ozone is lost in the tube centre where in contrast the electron and oxygen atom densities are maximal. Two models were used to analyse the obtained results. The first one is a kinetic 1D model for the processes occurring near the tube walls with the participation of the main particles: O( 3 P), O 2 , O 2 ( 1 Δ g ) and O 3 molecules in different vibrational states. The agreement of O 3 and O( 3 P) density profiles and T V calculated in the model with observed ones was reached by varying the single model parameter-ozone production probability (γ O 3 ) on the quartz tube surface on the assumption that O 3 production occurs mainly in the surface recombination of physisorbed O( 3 P) and O 2 . The phenomenological model of the surface processes with the participation of oxygen atoms and molecules including singlet oxygen molecules was also considered to analyse γ O 3 data obtained in the kinetic model. A good agreement between the experimental data and the data of both models-the kinetic 1D model and the phenomenological surface model-was obtained in the full range of the studied conditions that allowed consideration of the ozone surface production mechanism in more detail. The important role of singlet oxygen in ozone surface production was shown. The O 3 surface production rate directly depends on the density of physisorbed oxygen atoms and molecules and can be high with increasing pressure and energy inputted into plasma while simultaneously keeping the surface temperature low enough. Using the special discharge cell design, such an approach opens up

  19. Atmospheric chemistry of isoflurane, desflurane, and sevoflurane: kinetics and mechanisms of reactions with chlorine atoms and OH radicals and global warming potentials.

    Science.gov (United States)

    Sulbaek Andersen, Mads P; Nielsen, Ole J; Karpichev, Boris; Wallington, Timothy J; Sander, Stanley P

    2012-06-21

    The smog chamber/Fourier-transform infrared spectroscopy (FTIR) technique was used to measure the rate coefficients k(Cl + CF(3)CHClOCHF(2), isoflurane) = (4.5 ± 0.8) × 10(-15), k(Cl + CF(3)CHFOCHF(2), desflurane) = (1.0 ± 0.3) × 10(-15), k(Cl + (CF(3))(2)CHOCH(2)F, sevoflurane) = (1.1 ± 0.1) × 10(-13), and k(OH + (CF(3))(2)CHOCH(2)F) = (3.5 ± 0.7) × 10(-14) cm(3) molecule(-1) in 700 Torr of N(2)/air diluent at 295 ± 2 K. An upper limit of 6 × 10(-17) cm(3) molecule(-1) was established for k(Cl + (CF(3))(2)CHOC(O)F). The laser photolysis/laser-induced fluorescence (LP/LIF) technique was employed to determine hydroxyl radical rate coefficients as a function of temperature (241-298 K): k(OH + CF(3)CHFOCHF(2)) = (7.05 ± 1.80) × 10(-13) exp[-(1551 ± 72)/T] cm(3) molecule(-1); k(296 ± 1 K) = (3.73 ± 0.08) × 10(-15) cm(3) molecule(-1), and k(OH + (CF(3))(2)CHOCH(2)F) = (9.98 ± 3.24) × 10(-13) exp[-(969 ± 82)/T] cm(3) molecule(-1); k(298 ± 1 K) = (3.94 ± 0.30) × 10(-14) cm(3) molecule(-1). The rate coefficient of k(OH + CF(3)CHClOCHF(2), 296 ± 1 K) = (1.45 ± 0.16) × 10(-14) cm(3) molecule(-1) was also determined. Chlorine atoms react with CF(3)CHFOCHF(2) via H-abstraction to give CF(3)CFOCHF(2) and CF(3)CHFOCF(2) radicals in yields of approximately 83% and 17%. The major atmospheric fate of the CF(3)C(O)FOCHF(2) alkoxy radical is decomposition via elimination of CF(3) to give FC(O)OCHF(2) and is unaffected by the method used to generate the CF(3)C(O)FOCHF(2) radicals. CF(3)CHFOCF(2) radicals add O(2) and are converted by subsequent reactions into CF(3)CHFOCF(2)O alkoxy radicals, which decompose to give COF(2) and CF(3)CHFO radicals. In 700 Torr of air 82% of CF(3)CHFO radicals undergo C-C scission to yield HC(O)F and CF(3) radicals with the remaining 18% reacting with O(2) to give CF(3)C(O)F. Atmospheric oxidation of (CF(3))(2)CHOCH(2)F gives (CF(3))(2)CHOC(O)F in a molar yield of 93 ± 6% with CF(3)C(O)CF(3) and HCOF as minor products. The IR

  20. Atom

    International Nuclear Information System (INIS)

    Auffray, J.P.

    1997-01-01

    The atom through centuries, has been imagined, described, explored, then accelerated, combined...But what happens truly inside the atom? And what are mechanisms who allow its stability? Physicist and historian of sciences, Jean-Paul Auffray explains that these questions are to the heart of the modern physics and it brings them a new lighting. (N.C.)

  1. Potentiometric investigation into complexing of Pr,Eu,Yb with new. beta. -diketones containing oxygen atom in fluorinated radical

    Energy Technology Data Exchange (ETDEWEB)

    Gritsenko, T.V.; Lozinskij, M.O.; Panyushkin, V.T.; Fialkov, Yu.A.; Berenblit, V.V. (Kubanskij Gosudarstvennyj Univ., Krasnodar (USSR); AN Ukrainskoj SSR, Kiev. Inst. Organicheskoj Khimii)

    1983-01-01

    Potentiometric method in the aqueous-methanol media at 25 deg and ionic torce of 0.15 (NaCl) has been used to determine the constants of acidic dissociation of the next ..beta..-diketones; Rsub(F)-CO-CHsub(2)-CO-R, where R=-C/sub 6/H/sub 5/, Rsub(F) C/sub 3/F/sub 7/OCF(CF/sub 3/) - (1), CF/sub 3/O(CF/sub 2/)/sub 3/OCF(CF/sub 3/) - (2), CF/sub 3/O(CF/sub 2/O)/sub 4/CF/sub 2/ - (3), CF/sub 3/O(CF/sub 2/)/sub 2/ - (4) and R=-C/sub 4/H/sub 3/S, Rsub(F) CF/sub 3/O(CF/sub 2/)/sub 3/OCF(CF/sub 3/) - (5), CF/sub 3/O(CF/sub 2/O)/sub 4/CF/sub 2/ - (6). Synthesis of the 1-3, 5, 6 is described. Stability constants of Pr/sup 3 +/, Eu/sup 3 +/, Yb/sup 3 +/ with 1-6 are calculated. Stability of the complexes for the each ..beta..-diketone increases in Pr-Eu-Yb series. Correlation between stability of the chelates and acidic properties of the ..beta..-diketonates is traced for the complexes of one metal with different ligands. Thus, the acidic properties of the ..beta..-diketones increase in the 1, 6-4 series; stability of their complexes with rare earths decreases in such order.

  2. Potentiometric investigation into complexing of Pr,Eu,Yb with new β-diketones containing oxygen atom in fluorinated radical

    International Nuclear Information System (INIS)

    Gritsenko, T.V.; Lozinskij, M.O.; Panyushkin, V.T.; Fialkov, Yu.A.; Berenblit, V.V.; AN Ukrainskoj SSR, Kiev. Inst. Organicheskoj Khimii)

    1983-01-01

    Potentiometric method in the aqueous-methanol media at 25 deg and ionic torce of 0.15 (NaCl) has been used to determine the constants of acidic dissociation of the next β-diketones; Rsub(F)-CO-CHsub(2)-CO-R, where R=-C 6 H 5 , Rsub(F) C 3 F 7 OCF(CF 3 ) - (1), CF 3 O(CF 2 ) 3 OCF(CF 3 ) - (2), CF 3 O(CF 2 O) 4 CF 2 - (3), CF 3 O(CF 2 ) 2 - (4) and R=-C 4 H 3 S, Rsub(F) CF 3 O(CF 2 ) 3 OCF(CF 3 ) - (5), CF 3 O(CF 2 O) 4 CF 2 - (6). Synthesis of the 1-3, 5, 6 is described. Stability constants of Pr 3+ , Eu 3+ , Yb 3+ with 1-6 are calculated. Stability of the complexes for the each β-diketone increases in Pr-Eu-Yb series. Correlation between stability of the chelates and acidic properties of the β-diketonates is traced for the complexes of one metal with different ligands. Thus, the acidic properties of the β-diketones increase in the 1, 6-4 series; stability of their complexes with rare earths decreases in such order

  3. Force-field parameters of the Psi and Phi around glycosidic bonds to oxygen and sulfur atoms.

    Science.gov (United States)

    Saito, Minoru; Okazaki, Isao

    2009-12-01

    The Psi and Phi torsion angles around glycosidic bonds in a glycoside chain are the most important determinants of the conformation of a glycoside chain. We determined force-field parameters for Psi and Phi torsion angles around a glycosidic bond bridged by a sulfur atom, as well as a bond bridged by an oxygen atom as a preparation for the next study, i.e., molecular dynamics free energy calculations for protein-sugar and protein-inhibitor complexes. First, we extracted the Psi or Phi torsion energy component from a quantum mechanics (QM) total energy by subtracting all the molecular mechanics (MM) force-field components except for the Psi or Phi torsion angle. The Psi and Phi energy components extracted (hereafter called "the remaining energy components") were calculated for simple sugar models and plotted as functions of the Psi and Phi angles. The remaining energy component curves of Psi and Phi were well represented by the torsion force-field functions consisting of four and three cosine functions, respectively. To confirm the reliability of the force-field parameters and to confirm its compatibility with other force-fields, we calculated adiabatic potential curves as functions of Psi and Phi for the model glycosides by adopting the Psi and Phi force-field parameters obtained and by energetically optimizing other degrees of freedom. The MM potential energy curves obtained for Psi and Phi well represented the QM adiabatic curves and also these curves' differences with regard to the glycosidic oxygen and sulfur atoms. Our Psi and Phi force-fields of glycosidic oxygen gave MM potential energy curves that more closely represented the respective QM curves than did those of the recently developed GLYCAM force-field. (c) 2009 Wiley Periodicals, Inc.

  4. First-principles studies on vacancy-modified interstitial diffusion mechanism of oxygen in nickel, associated with large-scale atomic simulation techniques

    International Nuclear Information System (INIS)

    Fang, H. Z.; Shang, S. L.; Wang, Y.; Liu, Z. K.; Alfonso, D.; Alman, D. E.; Shin, Y. K.; Zou, C. Y.; Duin, A. C. T. van; Lei, Y. K.; Wang, G. F.

    2014-01-01

    This paper is concerned with the prediction of oxygen diffusivities in fcc nickel from first-principles calculations and large-scale atomic simulations. Considering only the interstitial octahedral to tetrahedral to octahedral minimum energy pathway for oxygen diffusion in fcc lattice, greatly underestimates the migration barrier and overestimates the diffusivities by several orders of magnitude. The results indicate that vacancies in the Ni-lattice significantly impact the migration barrier of oxygen in nickel. Incorporation of the effect of vacancies results in predicted diffusivities consistent with available experimental data. First-principles calculations show that at high temperatures the vacancy concentration is comparable to the oxygen solubility, and there is a strong binding energy and a redistribution of charge density between the oxygen atom and vacancy. Consequently, there is a strong attraction between the oxygen and vacancy in the Ni lattice, which impacts diffusion

  5. Single Cobalt Atoms with Precise N-Coordination as Superior Oxygen Reduction Reaction Catalysts.

    Science.gov (United States)

    Yin, Peiqun; Yao, Tao; Wu, Yuen; Zheng, Lirong; Lin, Yue; Liu, Wei; Ju, Huanxin; Zhu, Junfa; Hong, Xun; Deng, Zhaoxiang; Zhou, Gang; Wei, Shiqiang; Li, Yadong

    2016-08-26

    A new strategy for achieving stable Co single atoms (SAs) on nitrogen-doped porous carbon with high metal loading over 4 wt % is reported. The strategy is based on a pyrolysis process of predesigned bimetallic Zn/Co metal-organic frameworks, during which Co can be reduced by carbonization of the organic linker and Zn is selectively evaporated away at high temperatures above 800 °C. The spherical aberration correction electron microscopy and extended X-ray absorption fine structure measurements both confirm the atomic dispersion of Co atoms stabilized by as-generated N-doped porous carbon. Surprisingly, the obtained Co-Nx single sites exhibit superior ORR performance with a half-wave potential (0.881 V) that is more positive than commercial Pt/C (0.811 V) and most reported non-precious metal catalysts. Durability tests revealed that the Co single atoms exhibit outstanding chemical stability during electrocatalysis and thermal stability that resists sintering at 900 °C. Our findings open up a new routine for general and practical synthesis of a variety of materials bearing single atoms, which could facilitate new discoveries at the atomic scale in condensed materials. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Effects of iron salts and haemosiderin from a thalassaemia patient on oxygen radical damage as measured in the comet assay

    NARCIS (Netherlands)

    Anderson, D.; Yardley-Jones, A.; Hambly, R.J.; Vives-Bauza, C.; Smykatz-Kloss, V.; Chua-anusorn, W.; Webb, J.

    2000-01-01

    Thalassaemia is a group of genetic diseases where haemoglobin synthesis is impaired. This chronic anaemia leads to increased dietary iron absorption, which develops into iron overload pathology. Treatment through regular transfusions increases oxygen capacity but also provides iron through the red

  7. Spin accumulation in Si channels using CoFe/MgO/Si and CoFe/AlOx/Si tunnel contacts with high quality tunnel barriers prepared by radical-oxygen annealing

    International Nuclear Information System (INIS)

    Akushichi, T.; Shuto, Y.; Sugahara, S.; Takamura, Y.

    2015-01-01

    We investigate spin injection into Si channels using three-terminal spin-accumulation (3T-SA) devices with high-quality CoFe/MgO/n-Si and CoFe/AlO x /n-Si tunnel spin-injectors whose tunnel barriers are formed by radical oxidation of Mg and Al thin films deposited on Si(100) substrates and successive annealing under radical-oxygen exposure. When the MgO and AlO x barriers are not treated by the radical-oxygen annealing, the Hanle-effect signals obtained from the 3T-SA devices are closely fitted by a single Lorentz function representing a signal due to trap spins. On the other hand, when the tunnel barriers are annealed under radical-oxygen exposure, the Hanle-effect signals can be accurately fitted by the superposition of a Lorentz function and a non-Lorentz function representing a signal due to accumulated spins in the Si channel. These results suggest that the quality improvement of tunnel barriers treated by radical-oxygen annealing is highly effective for spin-injection into Si channels

  8. Comparison of NO titration and fiber optics catalytic probes for determination of neutral oxygen atom concentration in plasmas and postglows

    International Nuclear Information System (INIS)

    Mozetic, Miran; Ricard, Andre; Babic, Dusan; Poberaj, Igor; Levaton, Jacque; Monna, Virginie; Cvelbar, Uros

    2003-01-01

    A comparative study of two different absolute methods NO titration and fiber optics catalytic probe (FOCP) for determination of neutral oxygen atom density is presented. Both methods were simultaneously applied for measurements of O density in a postglow of an Ar/O 2 plasma created by a surfatron microwave generator with the frequency of 2.45 GHz an adjustable output power between 30 and 160 W. It was found that the two methods gave similar results. The advantages of FOCP were found to be as follows: it is a nondestructive method, it enables real time measuring of the O density, it does not require any toxic gas, and it is much faster than NO titration. The advantage of NO titration was found to be the ability to measure O density in a large range of dissociation of oxygen molecules

  9. Intramolecular addition of benzylic radicals onto ketenimines. Synthesis of 2-alkylindoles.

    Science.gov (United States)

    Alajarín, Mateo; Vidal, Angel; Ortín, María-Mar

    2003-12-07

    The inter- and intramolecular addition of free radicals onto ketenimines is studied. All the attempts to add intermolecularly several silicon, oxygen or carbon centered radicals to N-(4-methylphenyl)-C,C-diphenyl ketenimine were unsuccessful. In contrast, the intramolecular addition of benzylic radicals, generated from xanthates, onto the central carbon of a ketenimine function with its N atom linked to the ortho position of the aromatic ring occurred under a variety of reaction conditions. These intramolecular cyclizations provide a novel radical-mediated synthesis of 2-alkylindoles.

  10. High-performance liquid chromatographic method to evaluate the hydrogen atom transfer during reaction between 1,1-diphenyl-2-picryl-hydrazyl radical and antioxidants

    Energy Technology Data Exchange (ETDEWEB)

    Boudier, Ariane; Tournebize, Juliana [CITHEFOR - EA 3452, Faculte de Pharmacie, Nancy-Universite, 5 Rue Albert Lebrun, BP 80403, 54001 Nancy Cedex (France); Bartosz, Grzegorz [Department of Molecular Biophysics, University of Lodz, Lodz (Poland); El Hani, Safae; Bengueddour, Rachid [Laboratoire de Nutrition et Sante, Biology Department, Faculty of Sciences, Ibn Tofail University, Kenitra (Morocco); Sapin-Minet, Anne [CITHEFOR - EA 3452, Faculte de Pharmacie, Nancy-Universite, 5 Rue Albert Lebrun, BP 80403, 54001 Nancy Cedex (France); Leroy, Pierre, E-mail: pierre.leroy@pharma.uhp-nancy.fr [CITHEFOR - EA 3452, Faculte de Pharmacie, Nancy-Universite, 5 Rue Albert Lebrun, BP 80403, 54001 Nancy Cedex (France)

    2012-01-20

    Highlights: Black-Right-Pointing-Pointer Both 1,1-diphenyl-2-picrylhydrazyl radical and its product measurement by HPLC. Black-Right-Pointing-Pointer Lowest limit of detection by monitoring 1,1-diphenyl-2-picryl-hydrazine. Black-Right-Pointing-Pointer Adsorption problem of the radical on HPLC parts have been pointed out. - Abstract: 1,1-Diphenyl-2-picrylhydrazyl (DPPH{center_dot}) is a stable nitrogen centred radical widely used to evaluate direct radical scavenging properties of various synthetic or natural antioxidants (AOs). The bleaching rate of DPPH{center_dot} absorbance at 515 nm is usually monitored for this purpose. In order to avoid the interference of complex coloured natural products used as antioxidant supplements or cosmetics, HPLC systems have been reported as alternative techniques to spectrophotometry. They also rely upon measurement of DPPH{center_dot} quenching rate and none of them permits to identify and measure 1,1-diphenyl-2-picryl-hydrazine (DPPH-H), the reduced product of DPPH{center_dot} resulting from hydrogen atom transfer (HAT), which is the main mechanism of the reaction between DPPH{center_dot} and AOs. We presently report an HPLC method devoted to the simultaneous measurement of DPPH{center_dot} and DPPH-H. Both were fully separated on a C18 column eluted with acetonitrile-10 mM ammonium citrate buffer pH 6.8 (70:30, v/v) and detected at 330 nm. Adsorption process of DPPH{center_dot} onto materials of the HPLC system was pointed out. Consequently, the linearity range observed for DPPH{center_dot} was restricted, thus a much lower limit of detection was obtained for DPPH-H than for DPPH{center_dot} using standards (0.02 and 14 {mu}M, respectively). The method was applied to three commonly used AOs, i.e. Trolox{sup Registered-Sign }, ascorbic acid and GSH, and compared with spectrophotometry. Further application to complex matrices (cell culture media, vegetal extracts) and nanomaterials demonstrated (i) its usefulness because of

  11. A Space Experiment to Measure the Atomic Oxygen Erosion of Polymers and Demonstrate a Technique to Identify Sources of Silicone Contamination

    Science.gov (United States)

    Banks, Bruce A.; deGroh, Kim K.; Baney-Barton, Elyse; Sechkar, Edward A.; Hunt, Patricia K.; Willoughby, Alan; Bemer, Meagan; Hope, Stephanie; Koo, Julie; Kaminski, Carolyn; hide

    1999-01-01

    A low Earth orbital space experiment entitled, "Polymers Erosion And Contamination Experiment", (PEACE) has been designed as a Get-Away Special (GAS Can) experiment to be accommodated as a Shuttle in-bay environmental exposure experiment. The first objective is to measure the atomic oxygen erosion yields of approximately 40 different polymeric materials by mass loss and erosion measurements using atomic force microscopy. The second objective is to evaluate the capability of identifying sources of silicone contamination through the use of a pin-hole contamination camera which utilizes environmental atomic oxygen to produce a contaminant source image on an optical substrate.

  12. Oxygen toxicity

    Directory of Open Access Journals (Sweden)

    C. A. van der Westhuizen

    1990-07-01

    Full Text Available Oxygen has been discovered about 200 years ago. Since then the vital physiological involvement of oxygen in various biologi­cal processes, mainly energy production, has been established. However, in the body molecular oxygen can be converted to toxic oxygen metabolites such as superoxide anion, hydrogen peroxide, the hydroxyl radical and singlet oxygen. These toxic metabolites are produced mainly in the mitochondria, plasma membranes and endoplasmic reticulum.

  13. BODIPY-pyrene and perylene dyads as heavy atom-free singlet oxygen sensitizers

    KAUST Repository

    Filatov, Mikhail A.

    2018-02-23

    Dyads combining BODIPY as an electron acceptor and pyrene or perylene as electron donor subunits were prepared and studied their photophysical properties studied by steady-state and transient spectroscopy. Depending on the structure of the subunits and polarity of the media, the dyads show either bright fluorescence or photo-induced electron transfer (PeT) in solution. Charge-transfer (CT) states formed as a result of PeT and were found to yield triplet excited states of the BODIPY. In the presence of molecular oxygen, the dyads sensitize singlet oxygen (1O2) with quantum yields of up to 0.75.

  14. BODIPY-pyrene and perylene dyads as heavy atom-free singlet oxygen sensitizers

    KAUST Repository

    Filatov, Mikhail A.; Karuthedath, Safakath; Polestshuk, Pavel M.; Callaghan, Susan; Flanagan, Keith J.; Wiesner, Thomas; Laquai, Fré dé ric; Senge, Mathias O.

    2018-01-01

    Dyads combining BODIPY as an electron acceptor and pyrene or perylene as electron donor subunits were prepared and studied their photophysical properties studied by steady-state and transient spectroscopy. Depending on the structure of the subunits and polarity of the media, the dyads show either bright fluorescence or photo-induced electron transfer (PeT) in solution. Charge-transfer (CT) states formed as a result of PeT and were found to yield triplet excited states of the BODIPY. In the presence of molecular oxygen, the dyads sensitize singlet oxygen (1O2) with quantum yields of up to 0.75.

  15. High-temperature shock tube and modeling studies on the reactions of methanol with D-atoms and CH3-radicals.

    Science.gov (United States)

    Peukert, S L; Michael, J V

    2013-10-10

    The shock tube technique has been used to study the hydrogen abstraction reactions D + CH3OH → CH2O + H + HD (A) and CH3 + CH3OH → CH2O + H + CH4 (B). For reaction A, the experiments span a T-range of 1016 K ≤ T ≤ 1325 K, at pressures 0.25 bar ≤ P ≤ 0.46 bar. The experiments on reaction B, CH3 + CH3OH, cover a T-range of 1138 K ≤ T ≤ 1270 K, at pressures around 0.40 bar. Reflected shock tube experiments, monitoring the depletion of D-atoms by applying D-atom atomic resonance absorption spectrometry (ARAS), were performed on reaction A using gas mixtures of C2D5I and CH3OH in Kr bath gas. C2D5I was used as precursor for D-atoms. For reaction B, reflected shock tube experiments monitoring H-atom formation with H-ARAS, were carried out using gas mixtures of diacetyl ((CH3CO)2) and CH3OH in Kr bath gas. (CH3CO)2 was used as the source of CH3-radicals. Detailed reaction models were assembled to fit the D-atom and H-atom time profiles in order to obtain experimental rate constants for reactions A and B. Total rate constants from the present experiments on D + CH3OH and CH3 + CH3OH can be represented by the Arrhenius equations kA(T) = 1.51 × 10(-10) exp(-3843 K/T) cm(3) molecules(-1) s(-1) (1016 K ≤ T ≤ 1325 K) and kB(T) = 9.62 × 10(-12) exp(-7477 K/T) cm(3) molecules(-1) s(-1) (1138 K ≤ T ≤ 1270 K). The experimentally obtained rate constants were compared with available rate data from the literature. The results from quantum chemical studies on reaction A were found to be in good agreement with the present results. The present work represents the first direct experimental study on these bimolecular reactions at combustion temperatures and is important to the high-temperature oxidation of CH3OH.

  16. Crystalline TiO{sub 2} grafted with poly(2-methacryloyloxyethyl phosphorylcholine) via surface-initiated atom-transfer radical polymerization

    Energy Technology Data Exchange (ETDEWEB)

    Zhao Yuancong; Tu Qiufen; Wang Jin; Huang Qiongjian [Key Lab. of Advanced Technology for Materials, Education Ministry, School of Material Science and Technology of Southwest Jiaotong University, Chengdu, Sichuan (China); Huang Nan, E-mail: zhaoyc7320@163.com [Key Lab. of Advanced Technology for Materials, Education Ministry, School of Material Science and Technology of Southwest Jiaotong University, Chengdu, Sichuan (China)

    2010-12-15

    Crystalline TiO{sub 2} films were prepared by unbalanced magnetron sputtering and the structure was confirmed by XRD. An organic layer of 11-hydroxyundecylphosphonic acid (HUPA) was prepared on the TiO{sub 2} films by self-assembling, and the HUPA on TiO{sub 2} films was confirmed by FTIR analysis. Simultaneously, hydroxyl groups were introduced in the phosphonic acid molecules to provide a functionality for further chemical modification. 2-Methacryloyloxyethyl phosphorylcholine (MPC), a biomimetic monomer, was chemically grafted on the HUPA surfaces at room temperature by surface-initiated atom-transfer radical polymerization. The surface characters of TiO{sub 2} films modified by poly-MPC were confirmed by FTIR, XPS and SEM analysis. Platelet adhesion experiment revealed that poly-MPC modified surface was effective to inhibit platelet adhesion in vitro.

  17. Preparation of molecularly imprinted nanoparticles with superparamagnetic susceptibility through atom transfer radical emulsion polymerization for the selective recognition of tetracycline from aqueous medium

    International Nuclear Information System (INIS)

    Dai, Jiangdong; Pan, Jianming; Xu, Longcheng; Li, Xiuxiu; Zhou, Zhiping; Zhang, Rongxian; Yan, Yongsheng

    2012-01-01

    Highlights: ► Atom transfer radical emulsion polymerization is a “living” and green technique. ► Nanoparticles can overcome mass transfer limitations and improve accessibility. ► Molecular imprinted nanoparticles with magnetic property for fast separation. ► The performance of imprinted nanoparticles was investigated in detail. ► Nanoparticles were used to selective recognize Tetracycline from water medium. - Abstract: In the work, we reported an effective method for the preparation of molecularly imprinted nanoparticles with superparamagnetic susceptibility through atom transfer radical emulsion polymerization (ATREP), and then as-prepared magnetic molecularly imprinted nanoparticles (MMINs) were evaluated as adsorbents for selective recognition of tetracycline (TC) molecules from aqueous medium. The resulting nanoparticles were characterized by FT-IR, TGA, VSM, SEM and TEM. The results demonstrated MMINs with a narrow diameter distribution were cross-linked with modified Fe 3 O 4 particles, composed of imprinted layer and exhibited good magnetic sensitivity, magnetic and thermal stability. Batch rebinding studies were carried out to determine the specific adsorption equilibrium, kinetics, and selective recognition. The estimated adsorption capacity of MMINs towards TC by the Langmuir isotherm model was 12.10 mg g −1 at 298 K, which was 6.33 times higher than that of magnetic non-molecularly imprinted nanoparticles (MNINs). The kinetic property of MMINs was well-described by the pseudo-second-order rate equation. The results of selective recognition experiments demonstrated outstanding affinity and selectivity towards TC over competitive antibiotics. The reusability of MMINs showed no obviously deterioration at least five repeated cycles in performance. In addition, the MMINs prepared were successfully applied to the extraction of TC from the spiked pork sample.

  18. Preparation of molecularly imprinted nanoparticles with superparamagnetic susceptibility through atom transfer radical emulsion polymerization for the selective recognition of tetracycline from aqueous medium

    Energy Technology Data Exchange (ETDEWEB)

    Dai, Jiangdong; Pan, Jianming; Xu, Longcheng; Li, Xiuxiu [School of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang 212013 (China); Zhou, Zhiping [School of Material Science and Engineering, Jiangsu University, Zhenjiang 212013 (China); Zhang, Rongxian [School of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang 212013 (China); Yan, Yongsheng, E-mail: djdxxx123@163.com [School of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang 212013 (China); State Key Laboratory of Natural and Biomimetic Drugs, Peking University, Beijing, 100191 (China)

    2012-02-29

    Highlights: Black-Right-Pointing-Pointer Atom transfer radical emulsion polymerization is a 'living' and green technique. Black-Right-Pointing-Pointer Nanoparticles can overcome mass transfer limitations and improve accessibility. Black-Right-Pointing-Pointer Molecular imprinted nanoparticles with magnetic property for fast separation. Black-Right-Pointing-Pointer The performance of imprinted nanoparticles was investigated in detail. Black-Right-Pointing-Pointer Nanoparticles were used to selective recognize Tetracycline from water medium. - Abstract: In the work, we reported an effective method for the preparation of molecularly imprinted nanoparticles with superparamagnetic susceptibility through atom transfer radical emulsion polymerization (ATREP), and then as-prepared magnetic molecularly imprinted nanoparticles (MMINs) were evaluated as adsorbents for selective recognition of tetracycline (TC) molecules from aqueous medium. The resulting nanoparticles were characterized by FT-IR, TGA, VSM, SEM and TEM. The results demonstrated MMINs with a narrow diameter distribution were cross-linked with modified Fe{sub 3}O{sub 4} particles, composed of imprinted layer and exhibited good magnetic sensitivity, magnetic and thermal stability. Batch rebinding studies were carried out to determine the specific adsorption equilibrium, kinetics, and selective recognition. The estimated adsorption capacity of MMINs towards TC by the Langmuir isotherm model was 12.10 mg g{sup -1} at 298 K, which was 6.33 times higher than that of magnetic non-molecularly imprinted nanoparticles (MNINs). The kinetic property of MMINs was well-described by the pseudo-second-order rate equation. The results of selective recognition experiments demonstrated outstanding affinity and selectivity towards TC over competitive antibiotics. The reusability of MMINs showed no obviously deterioration at least five repeated cycles in performance. In addition, the MMINs prepared were successfully

  19. Modelling of the heat transfer during oxygen atoms recombination on metallic surfaces in a plasma reactor

    NARCIS (Netherlands)

    Cavadias, S; Cauquot, P; Amouroux, J

    1997-01-01

    Space shuttle overheating during the re-entry phase, due to catalytic oxygen recombination on the thermal protection system, is a problem of practical and theoretical interest. The energy transfer is characterised by the product of the accommodation and the recombination coefficients. Previous

  20. A barrier-free atomic radical-molecule reaction: N (2D) NO2 (2A1) mechanistic study

    Science.gov (United States)

    Zuo, Ming-Hui; Liu, Hui-Ling; Huang, Xu-Ri; Zhan, Jin-Hui; Sun, Chia-Chung

    The reaction of N (2D) radical with NO2 molecule has been studied theoretically using density functional theory and ab initio quantum chemistry method. Singlet electronic state [N2O2] potential energy surfaces (PES) are calculated at the CCSD(T)/aug-cc-pVDZ//B3LYP/6-311+G(d) + ZPE and G3B3 levels of theory. All the involved transition states for generation of (2NO) and (O2 + N2) lie much lower than the reactants. Thus, the novel reaction N + NO2 can proceed effectively even at low temperatures and it is expected to play a role in both combustion and interstellar processes. On the basis of the analysis of the kinetics of all pathways through which the reactions proceed, we expect that the competitive power of reaction pathways may vary with experimental conditions for the title reaction.

  1. Nature of oxygen containing radicals in radiation chemistry and photochemistry of aqueous solutions. Annual progress report, September 1978--July 1979

    International Nuclear Information System (INIS)

    Czapski, G.

    1979-01-01

    The proposed research is a continuation of the work conducted under this contract and is outlined. During this year, the main emphasis will be given to study further the properties of HO 2 and O 2 - and OH, mainly in their role in biological systems. We will continue to study and elucidate how O 2 - reacts in biological systems. The toxicity of O 2 - is quite well established, but the mechanism is still obscure. The Haber Weiss reaction most probably can not account for the toxicity of O 2 - nor for the formation of singlet oxygen, nor of OH. We will study if reduction of Fe 3+ complexes by O 2 - in biological systems does catalyze the Haber Weiss reaction and if OH is formed in this mechanism. The role of oxygen, radiosensitizers in radiation damage of bacteriophages and cells will be further studied, as well as on E. Coli and Enzymes. We will try to elucidate the formation and role of OH, O 2 - and O 2 in these systems as well as the relative contribution of endogenous and exogenous damage, and the role of direct and indirect radiation damage to cells. We intend also to study if SOD (super oxide dismutase) does react only with O 2 - or also with biological peroxides (RO 2 ) and Hydroperoxides (RO 2 H). Further studies of O 2 - and O 2 with various cytochromes, and hemoglobins is planned

  2. Enhancement of alpha particles-induced cell transformation by oxygen free radicals and tumor necrosis factor released from phagocytes

    International Nuclear Information System (INIS)

    Gong Yifen; Guo Renfeng; Zhu Maoxiang; Shou Jiang; Ge Guixiu; Yang Zhihua; Hieber, L.; Peters, K.; Schippel, C.

    1997-01-01

    To illustrate the role of several endogenous factors released from phagocytes under chronic inflammation in radiation-induced cancer. C 3 T 10 T 1/2 and SHE cells were used as targets, and 238 Pu alpha source was used in alpha irradiation. The enhancement of TF in alpha particles-induced cell transformation by PMA-stimulated human blood and zymosan-stimulated U-937 cells was studied using formation of transformed foci. Transformation frequency (TF) of C 3 H 10 T 1/2 cells exposed to alpha particles of 0.5 Gy increased 2.1 and 2.8 fold by PMA-and PMA-stimulated neutrophils, respectively. TF of irradiated SHE cells at a dose of 0.5 Gy increased 12 fold by the addition of the supernatant of macrophage-like U-937 cell line. It was shown that TF of irradiated SHE cells at above dose increased 8 fold by the supernatant treated with anti-TNF-α could be subcultured continuously in vitro. The cells at 40 th passage and two lines of monoclone cells have the ability to develop malignant tumors in nude mice. The overdose of free radicals and TNF-α released from neutrophils and macrophages have played an important role in low dose radiation-induced cancer

  3. Fe Isolated Single Atoms on S, N Codoped Carbon by Copolymer Pyrolysis Strategy for Highly Efficient Oxygen Reduction Reaction.

    Science.gov (United States)

    Li, Qiheng; Chen, Wenxing; Xiao, Hai; Gong, Yue; Li, Zhi; Zheng, Lirong; Zheng, Xusheng; Yan, Wensheng; Cheong, Weng-Chon; Shen, Rongan; Fu, Ninghua; Gu, Lin; Zhuang, Zhongbin; Chen, Chen; Wang, Dingsheng; Peng, Qing; Li, Jun; Li, Yadong

    2018-06-01

    Heteroatom-doped Fe-NC catalyst has emerged as one of the most promising candidates to replace noble metal-based catalysts for highly efficient oxygen reduction reaction (ORR). However, delicate controls over their structure parameters to optimize the catalytic efficiency and molecular-level understandings of the catalytic mechanism are still challenging. Herein, a novel pyrrole-thiophene copolymer pyrolysis strategy to synthesize Fe-isolated single atoms on sulfur and nitrogen-codoped carbon (Fe-ISA/SNC) with controllable S, N doping is rationally designed. The catalytic efficiency of Fe-ISA/SNC shows a volcano-type curve with the increase of sulfur doping. The optimized Fe-ISA/SNC exhibits a half-wave potential of 0.896 V (vs reversible hydrogen electrode (RHE)), which is more positive than those of Fe-isolated single atoms on nitrogen codoped carbon (Fe-ISA/NC, 0.839 V), commercial Pt/C (0.841 V), and most reported nonprecious metal catalysts. Fe-ISA/SNC is methanol tolerable and shows negligible activity decay in alkaline condition during 15 000 voltage cycles. X-ray absorption fine structure analysis and density functional theory calculations reveal that the incorporated sulfur engineers the charges on N atoms surrounding the Fe reactive center. The enriched charge facilitates the rate-limiting reductive release of OH* and therefore improved the overall ORR efficiency. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Single Molecule Atomic Force Microscopy Studies of Photosensitized Singlet Oxygen Behavior on a DNA Origami Template

    DEFF Research Database (Denmark)

    Helmig, Sarah Wendelboe; Rotaru, Alexandru; Arian, Dumitru

    2010-01-01

    DNA origami, the folding of a long single-stranded DNA sequence (scaffold strand) by hundreds of short synthetic oligonucleotides (staple strands) into parallel aligned helices, is a highly efficient method to form advanced self-assembled DNA-architectures. Since molecules and various materials can...... be conjugated to each of the short staple strands, the origami method offers a unique possibility of arranging molecules and materials in well-defined positions on a structured surface. Here we combine the action of light with AFM and DNA nanostructures to study the production of singlet oxygen from a single...... photosensitizer molecule conjugated to a selected DNA origami staple strand on an origami structure. We demonstrate a distance-dependent oxidation of organic moieties incorporated in specific positions on DNA origami by singlet oxygen produced from a single photosensitizer located at the center of each origami....

  5. Inorganic-organic hybrid coatings on stainless steel by layer-by-layer deposition and surface-initiated atom-transfer-radical polymerization for combating biocorrosion.

    Science.gov (United States)

    Yuan, S J; Pehkonen, S O; Ting, Y P; Neoh, K G; Kang, E T

    2009-03-01

    To improve the biocorrosion resistance of stainless steel (SS) and to confer the bactericidal function on its surface for inhibiting bacterial adhesion and biofilm formation, well-defined inorganic-organic hybrid coatings, consisting of the inner compact titanium oxide multilayers and outer dense poly(vinyl-N-hexylpyridinium) brushes, were successfully developed. Nanostructured titanium oxide multilayer coatings were first built up on the SS substrates via the layer-by-layer sol-gel deposition process. The trichlorosilane coupling agent, containing the alkyl halide atom-transfer-radical polymerization (ATRP) initiator, was subsequently immobilized on the titanium oxide coatings for surface-initiated ATRP of 4-vinylpyridine (4VP). The pyridium nitrogen moieties of the covalently immobilized 4VP polymer, or P(4VP), brushes were quaternized with hexyl bromide to produce a high concentration of quaternary ammonium salt on the SS surfaces. The excellent antibacterial efficiency of the grafted polycations, poly(vinyl-N-pyridinium bromide), was revealed by viable cell counts and atomic force microscopy images of the surface. The effectiveness of the hybrid coatings in corrosion protection was verified by the Tafel plot and electrochemical impedance spectroscopy measurements.

  6. Free radical hydrogen atom abstraction from saturated hydrocarbons: A crossed-molecular-beams study of the reaction Cl + C{sub 3}H{sub 8} {yields} HCl + C{sub 3}H{sub 7}

    Energy Technology Data Exchange (ETDEWEB)

    Blank, D.A.; Hemmi, N.; Suits, A.G.; Lee, Y.T. [Lawrence Berkeley National Lab., CA (United States)

    1997-04-01

    The abstraction of hydrogen atoms from saturated hydrocarbons are reactions of fundamental importance in combustion as well as often being the rate limiting step in free radical substitution reactions. The authors have begun studying these reactions under single collision conditions using the crossed molecular beam technique on beamline 9.0.2.1, utilizing VUV undulator radiation to selectively ionize the scattered hydrocarbon free radical products (C{sub x}H{sub 2x+1}). The crossed molecular beam technique involves two reactant molecular beams fixed at 90{degrees}. The molecular beam sources are rotatable in the plane defined by the two beams. The scattered neutral products travel 12.0 cm where they are photoionized using the VUV undulator radiation, mass selected, and counted as a function of time. In the authors initial investigations they are using halogen atoms as protypical free radicals to abstract hydrogen atoms from small alkanes. Their first study has been looking at the reaction of Cl + propane {r_arrow} HCl + propyl radical. In their preliminary efforts the authors have measured the laboratory scattering angular distribution and time of flight spectra for the propyl radical products at collision energies of 9.6 kcal/mol and 14.9 kcal/mol.

  7. Atomic-Oxygen-Durable and Electrically-Conductive CNT-POSS-Polyimide Flexible Films for Space Applications.

    Science.gov (United States)

    Atar, Nurit; Grossman, Eitan; Gouzman, Irina; Bolker, Asaf; Murray, Vanessa J; Marshall, Brooks C; Qian, Min; Minton, Timothy K; Hanein, Yael

    2015-06-10

    In low Earth orbit (LEO), hazards such as atomic oxygen (AO) or electrostatic discharge (ESD) degrade polymeric materials, specifically, the extensively used polyimide (PI) Kapton. We prepared PI-based nanocomposite films that show both AO durability and ESD protection by incorporating polyhedral oligomeric silsesquioxane (POSS) and carbon nanotube (CNT) additives. The unique methods that are reported prevent CNT agglomeration and degradation of the CNT properties that are common in dispersion-based processes. The influence of the POSS content on the electrical, mechanical, and thermo-optical properties of the CNT-POSS-PI films was investigated and compared to those of control PI and CNT-PI films. CNT-POSS-PI films with 5 and 15 wt % POSS content exhibited sheet resistivities as low as 200 Ω/□, and these resistivities remained essentially unchanged after exposure to AO with a fluence of ∼2.3 × 10(20) O atoms cm(-2). CNT-POSS-PI films with 15 wt % POSS content exhibited an erosion yield of 4.8 × 10(-25) cm(3) O atom(-1) under 2.3 × 10(20) O atoms cm(-2) AO fluence, roughly one order of magnitude lower than that of pure PI films. The durability of the conductivity of the composite films was demonstrated by rolling film samples with a tight radius up to 300 times. The stability of the films to thermal cycling and ionizing radiation was also demonstrated. These properties make the prepared CNT-POSS-PI films with 15 wt % POSS content excellent candidates for applications where AO durability and electrical conductivity are required for flexible and thermally stable materials. Hence, they are suggested here for LEO applications such as the outer layers of spacecraft thermal blankets.

  8. RATE CONSTANTS FOR THE REACTIONS OF OH RADICALS AND CL ATOMS WITH DI-N-PROPYL ETHER AND DI-N-BUTYL ETHER AND THEIR DEUTERATED ANALOGS. (R825252)

    Science.gov (United States)

    Using relative rate methods, rate constants for the gas-phase reactions of OH radicals and Cl atoms with di-n-propyl ether, di-n-propyl ether-d14, di-n-butyl ether and di-n-butyl ether-d18 have been measured at 296 ? 2 K and atmos...

  9. Hetero-atom doped carbon nanotubes for dye degradation and oxygen reduction reaction

    Energy Technology Data Exchange (ETDEWEB)

    Nandan, Ravi, E-mail: aerawat27@gmail.com; Nanda, Karuna Kar [Materials Research Centre, Indian Institute of Science, Bangalore-560012 (India)

    2015-06-24

    We report the synthesis of nitrogen doped vertically aligned multi-walled (MWNCNTs) carbon nanotubes by pyrolysis and its catalytic performance for degradation of methylene blue (MB) dye & oxygen reduction reaction (ORR). The degradation of MB was monitored spectrophotometrically with time. Kinetic studies show the degradation of MB follows a first order kinetic with rate constant k=0.0178 min{sup −1}. The present rate constant is better than that reported for various supported/non-supported semiconducting nanomaterials. Further ORR performance in alkaline media makes MWNCNTs a promising cost-effective, fuel crossover tolerance, metal-free, eco-friendly cathode catalyst for direct alcohol fuel cell.

  10. Atmospheric plasma generates oxygen atoms as oxidizing species in aqueous solutions

    Czech Academy of Sciences Publication Activity Database

    Hefny, M.M.; Pattyn, C.; Lukeš, Petr; Benedikt, J.

    2016-01-01

    Roč. 49, č. 40 (2016), s. 404002 ISSN 0022-3727 R&D Projects: GA MŠk(CZ) LD14080 Grant - others:European Cooperation in Science and Technology(XE) COST TD1208 Institutional support: RVO:61389021 Keywords : atmospheric pressure plasma * transport of reactive species * reactive oxygen species * aqueous phase chemistry * plasma and liquids * phenol aqueous chemistry Subject RIV: BL - Plasma and Gas Discharge Physics Impact factor: 2.588, year: 2016 http://iopscience.iop.org/article/10.1088/0022-3727/49/40/404002

  11. THE PROTECTIVE ROLE OF VITAMIN E AGAINST OXYGEN FREE RADICAL AND DNA DAMAGE IN CHILDREN WITH β-THALASSEMIA MAJOR

    International Nuclear Information System (INIS)

    NASSAR, E.M.

    2008-01-01

    The present study aimed to determine the benefits of vitamin E as antioxidant supplement in β thalassemia children who are at risk of iron overload due to multiple blood transfusion and oxidative stress. Antioxidant markers, oxidative products, hematological parameters and biomarkers of cell damage were studied in 24 transfusion-dependent β -thalassemia children before and after treatment with vitamin E at a dose of 10 mg/kg /day for a period of four weeks. Plasma thiobarbituric acid reactive species (TBARS) and urinary 8-hydroxy-2 ' -deoxyguanosine (8-OHdG) were analyzed as oxidative markers, whereas the plasma vitamin E and the activities of the antioxidant enzymes glutathione peroxidase (GSH-Px), superoxide dismutase(SOD) and catalase were measured to show the antioxidant status of thalassemic children. All these parameters were also studied in 15 non-anemic healthy controls .The results showed that all the patients had increased signs of iron overload and cell damage that were obvious from the increase in serum iron, ferritin, alanine transaminases (ALT), aspartate transaminases (AST) and both total and direct bilirubin .The level of plasma vitamin E in the thalassemia patients were found to be significantly lower as compared to normal subjects (1.3 ± 0.7 and 3.14 ± 1.5 mg % , respectively). The activities of antioxidants enzymes, glutathione peroxidase and catalase in untreated β-thalassemic patients were found to be significantly (P<0.001) less than that of the normal subjects. However, SOD level was significantly increased. Markers of free radical injury such as TBARS , urinary 8-OHdG levels in thalassemic children were significantly higher than control levels . All these changes in the antioxidant status as well as the hematological parameters, iron overload and cell damage markers in β-thalassemia patients showed significant improvement after vitamin E supplementation. Vitamin E levels showed significant positive correlations with each of Hb, GSH

  12. Hydroxyl radical-PLIF measurements and accuracy investigation in high pressure gaseous hydrogen/gaseous oxygen combustion

    Science.gov (United States)

    Vaidyanathan, Aravind

    In-flow species concentration measurements in reacting flows at high pressures are needed both to improve the current understanding of the physical processes taking place and to validate predictive tools that are under development, for application to the design and optimization of a range of power plants from diesel to rocket engines. To date, non intrusive measurements have been based on calibrations determined from assumptions that were not sufficiently quantified to provide a clear understanding of the range of uncertainty associated with these measurements. The purpose of this work is to quantify the uncertainties associated with OH measurement in a oxygen-hydrogen system produced by a shear, coaxial injector typical of those used in rocket engines. Planar OH distributions are obtained providing instantaneous and averaged distribution that are required for both LES and RANS codes currently under development. This study has evaluated the uncertainties associated with OH measurement at 10, 27, 37 and 53 bar respectively. The total rms error for OH-PLIF measurements from eighteen different parameters was quantified and found as 21.9, 22.8, 22.5, and 22.9% at 10, 27, 37 and 53 bar respectively. These results are used by collaborators at Georgia Institute of Technology (LES), Pennsylvania State University (LES), University of Michigan (RANS) and NASA Marshall (RANS).

  13. Generation of Free Oxygen Atoms O(3P) in Solution by Photolysis of 4-Benzoylpyridine N-Oxide

    Energy Technology Data Exchange (ETDEWEB)

    Carraher, Jack M. [Ames Lab., Ames, IA (United States); Iowa State Univ., Ames, IA (United States); Bakac, Andreja [Ames Lab., Ames, IA (United States); Iowa State Univ., Ames, IA (United States)

    2014-08-04

    Laser flash photolysis of 4-benzoylpyridine N-oxide (BPyO) at 308 nm in aqueous solutions generates a triplet excited state 3BPyO* that absorbs strongly in the visible, λmax 490 and 380 nm. 3BPyO* decays with the rate law kdecay/s-1 = (3.3 ± 0.9) × 104 + (1.5 ± 0.2) × 109 [BPyO] to generate a mixture of isomeric hydroxylated benzoylpyridines, BPy(OH), in addition to small amounts of oxygen atoms, O(3P). Molecular oxygen quenches 3BPyO*, kQ = 1.4 × 109 M-1 s-1, but the yields of O(3P) increase in O2-saturated solutions to 36%. Other triplet quenchers have a similar effect, which rules out the observed 3BPyO* as a source of O(3P). It is concluded that O(3P) is produced from either 1BPyO* or a short-lived, unobserved, higher energy triplet generated directly from 1BPyO*. 3BPyO* is reduced by Fe2+ and by ABTS2- to the radical anion BPyO.- which exhibits a maximum at 510 nm, ε = 2200 M-1 cm-1. The anion engages in back electron transfer with ABTS.- with k = 1.7 × 109 M-1 s-1. The same species can be generated by reducing ground state BPyO with .C(CH3)2OH. The photochemistry of BPyO in acetonitrile is similar to that in aqueous solutions.

  14. First-Principles Study on the Structural and Electronic Properties of N Atoms Doped-Rutile TiO2 of Oxygen Vacancies

    Directory of Open Access Journals (Sweden)

    Zhong-Liang Zeng

    2015-01-01

    Full Text Available For the propose of considering the actual situation of electronic neutral, a simulation has been down on the basis of choosing the position of dual N and researching the oxygen vacancy. It is found that the reason why crystal material gets smaller is due to the emergence of impurity levels. By introducing the oxygen vacancy to the structure, the results show that while the oxygen vacancy is near the two nitrogen atoms which have a back to back position, its energy gets the lowest level and its structure gets the most stable state. From its energy band structure and density, the author finds that the impurity elements do not affect the migration of Fermi level while the oxygen vacancy has been increased. Instead of that, the conduction band of metal atoms moves to the Fermi level and then forms the N-type semiconductor material, but the photocatalytic activity is not as good as the dual N-doping state.

  15. Nature of oxygen containing radicals in radiation chemistry and photochemistry of aqueous solutions. Annual progress report, September 1979-July 1980

    International Nuclear Information System (INIS)

    Czapski, G.

    1980-01-01

    During this year, emphasis will be given on the properties of HO 2 and O 2 - and OH, mainly in their role in biological systems. We will continue to study and elucidate how O 2 - reacts in biological systems. The toxicity of O 2 - is quite well established but the mechanism is still obscure. One way O 2 - is toxic is that OH is formed from O 2 - through reduction of Fe 3+ , and subsequently the reaction of Fe 2+ with H 2 O 2 (Fenton reaction). This mechanism is sometimes called the Haber Weiss Reaction. We will study if reduction of Fe 3+ complexes by O 2 - in biological systems does catalyze the Haber Weiss reaction and if OH is formed in this mechanism. The role of oxygen, radiosensitizers in radiation damage of bacteriophages and cells will be further studied, as well as on E. coli and enzymes. Use of different mutants, such as ones with repair deficiencies, or others which are deficient in glutathione will help to elucidate the role of O 2 - and O 2 toxicity. We will try to elucidate the formation and role of OH, O 2 - and O 2 in these systems as well as the relative contribution of endogenous and exogenous damage, and the role of direct and indirect radiation damage to cells. As there is some doubt how and if SOD protects cells from irradiation as literature results show lots of conflict, we will try to clear this point, in studies with E. coli mutants, and adding SOD endogenously and exogenously. We also intend to study if SOD (super oxide dismutase) does react only with O 2 - or also with biological peroxides (RO 2 ) and hydroperoxides (RO 2 H). Further studies of O 2 - and O 2 with various cytochromes, and hemoglobins is planned

  16. Mid-latitude empirical model of the height distribution of atomic oxygen in the MLT region for different solar and geophysical conditions

    Science.gov (United States)

    Semenov, A.; Shefov, N.; Fadel, Kh.

    The model of altitude distributions of atomic oxygen in the region of the mesopause and lower thermosphere (MLT) is constructed on the basis of empirical models of variations of the intensities, temperatures and altitudes of maximum of the layers of the emissions of atomic oxygen at 557.7 nm, hydroxyl and Atmospheric system of molecular oxygen. An altitude concentration distribution of neutral components is determined on the basis of systematization of the long-term data of temperature of the middle atmosphere from rocket, nightglow and ionospheric measurements at heights of 30-110 km in middle latitudes. They include dependence on a season, solar activity and a long-term trend. Examples of results of calculation for different months of year for conditions of the lower and higher solar activity are presented. With increasing of solar activity, the height of a layer of a maximum of atomic oxygen becomes lower, and the thickness of the layer increases. There is a high correlation between characteristics of a layer of atomic oxygen and a maximum of temperature at heights of the mesopause and lower thermosphere. This work is supported by grant of ISTC No. 2274.

  17. Preparation of high-content hexagonal boron nitride composite film and characterization of atomic oxygen erosion resistance

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Yu; Li, Min; Gu, Yizhuo; Wang, Shaokai, E-mail: wsk@buaa.edu.cn; Zhang, Zuoguang

    2017-04-30

    Highlights: • Hexagonal boron nitride nanosheets can be well exfoliated with the help of nanofibrillated cellulose. • A carpet-like rough surface and distortion in crystal structure of h-BN are found in both h-BN film and h-BN/epoxy film after AO exposure. • H-BN/epoxy film exhibits a higher mass loss and erosion yield, different element content changes and chemical oxidations compared with h-BN film. - Abstract: Space aircrafts circling in low earth orbit are suffered from highly reactive atomic oxygen (AO). To shield AO, a flexible thin film with 80 wt.% hexagonal boron nitride (h-BN) and h-BN/epoxy film were fabricated through vacuum filtration and adding nanofibrillated cellulose fibers. H-BN nanosheets were hydroxylated for enhancing interaction in the films. Mass loss and erosion yield at accumulated AO fluence about 3.04 × 10{sup 20} atoms/cm{sup 2} were adopted to evaluate the AO resistance properties of the films. A carpet-like rough surface, chemical oxidations and change in crystal structure of h-BN were found after AO treatment, and the degrading mechanism was proposed. The mass loss and erosion yield under AO attack were compared between h-BN film and h-BN/epoxy film, and the comparison was also done for various types of shielding AO materials. Excellent AO resistance property of h-BN film is shown, and the reasons are analyzed.

  18. Oxidation of nitrite by a trans-dioxoruthenium(VI) complex: direct evidence for reversible oxygen atom transfer.

    Science.gov (United States)

    Man, Wai-Lun; Lam, William W Y; Wong, Wai-Yeung; Lau, Tai-Chu

    2006-11-15

    Reaction of trans-[Ru(VI)(L)(O)(2)](2+) (1, L = 1,12-dimethyl-3,4:9,10-dibenzo-1,12-diaza-5,8-dioxacyclopentadecane, a tetradentate macrocyclic ligand with N(2)O(2) donor atoms) with nitrite in aqueous solution or in H(2)O/CH(3)CN produces the corresponding (nitrato)oxoruthenium(IV) species, trans-[Ru(IV)(L)(O)(ONO(2))](+) (2), which then undergoes relatively slow aquation to give trans-[Ru(IV)(L)(O)(OH(2))](2+). These processes have been monitored by both ESI/MS and UV/vis spectrophotometry. The structure of trans-[Ru(IV)(L)(O)(ONO(2))](+) (2) has been determined by X-ray crystallography. The ruthenium center adopts a distorted octahedral geometry with the oxo and the nitrato ligands trans to each other. The Ru=O distance is 1.735(3) A, the Ru-ONO(2) distance is 2.163(4) A, and the Ru-O-NO(2) angle is 138.46(35) degrees . Reaction of trans-[Ru(VI)(L)((18)O)(2)](2+) (1-(18)O(2)) with N(16)O(2)(-) in H(2)O/CH(3)CN produces the (18)O-enriched (nitrato)oxoruthenium(IV) species 2-(18)O(2). Analysis of the ESI/MS spectrum of 2-(18)O(2) suggests that scrambling of the (18)O atoms has occurred. A mechanism that involves linkage isomerization of the nitrato ligand and reversible oxygen atom transfer is proposed.

  19. Theoretical insight into an empirical rule about organic corrosion inhibitors containing nitrogen, oxygen, and sulfur atoms

    Energy Technology Data Exchange (ETDEWEB)

    Guo, Lei, E-mail: cqglei@163.com [School of Material and Chemical Engieering, Tongren University, Tongren 554300 (China); Obot, Ime Bassey [Center of Research Excellence in Corrosion, King Fahd University of Petroleum and Minerals, Dhahran 31261 (Saudi Arabia); Zheng, Xingwen [Material Corrosion and Protection Key Laboratory of Sichuan province, Zigong 643000 (China); Shen, Xun [School of Material and Chemical Engieering, Tongren University, Tongren 554300 (China); Qiang, Yujie [Material Corrosion and Protection Key Laboratory of Sichuan province, Zigong 643000 (China); Kaya, Savaş; Kaya, Cemal [Department of Chemistry, Faculty of Science, Cumhuriyet University, Sivas 58140 (Turkey)

    2017-06-01

    Highlights: • We obtained the habit information of α-Fe obtained by the “Morphology” module. • The adsorption of pyrrole, furan, and thiophene on Fe(110) surface were studied by DFT calculations. • Our DFT modeling provided a reasonable micro-explanation to the empirical rule. - Abstract: Steel is an important material in industry. Adding heterocyclic organic compounds have proved to be very efficient for steel protection. There exists an empirical rule that the general trend in the inhibition efficiencies of molecules containing heteroatoms is such that O < N < S. However, an atomic-level insight into the inhibition mechanism is still lacked. Thus, in this work, density functional theory calculations was used to investigate the adsorption of three typical heterocyclic molecules, i.e., pyrrole, furan, and thiophene, on Fe(110) surface. The approach is illustrated by carrying out geometric optimization of inhibitors on the stable and most exposed plane of α-Fe. Some salient features such as charge density difference, changes of work function, density of states were detailedly described. The present study is helpful to understand the afore-mentioned experiment rule.

  20. Solar photolysis of ozone to singlet D oxygen atoms, O(1D)

    International Nuclear Information System (INIS)

    Blackburn, T.E.

    1984-01-01

    Ground level solar photolysis rate coefficients (jO 3 ) were measured for the photolysis of ozone by sunlight, (O 3 + hnu( 2 + O( 1 D)). The O( 1 D) atoms produced react with nitrous oxide (N 2 O) carrier gas to form higher oxides of nitrogen (NOx). Computer model predictions show that these are mainly N 2 O 5 and NO 3 . Seventy five days of data were taken during the summer of 1983, at Ann Arbor, Michigan, and are presented in the appendix. Over 390 clear air jO 3 values are correlated with effective ozone column densities, and 500 nm aerosol optical depths. The solar direct beam component of ozone photolysis was measured for the different aerosol optical depths, over two entire days from sun-up to sun-down. Temperature dependence of jO 3 was measured from 10 0 C to 39 0 C with good agreement to models. Comparison of jO 3 versus global and ultraviolet radiation are made under various ozone column densities and aerosol optical depths. A jO 3 -photometer was built using an interference filter to pass only ozone photolyzing light. Improvements to instrumental parts are shown for balloon and aircraft flyable payloads

  1. Poly(glycidyl methacrylate) grafted CdSe quantum dots by surface-initiated atom transfer radical polymerization: Novel synthesis, characterization, properties, and cytotoxicity studies

    Energy Technology Data Exchange (ETDEWEB)

    Bach, Long Giang; Islam, Md. Rafiqul [Department of Imaging System Engineering, Pukyong National University, Busan 608-737 (Korea, Republic of); Lee, Doh Chang [Department of Chemical and Biomolecular Engineering, KAIST Institute for the Nanocentury (KINC), Korea Advanced Institute of Science and Technology (KAIST), Daejeon 305-701 (Korea, Republic of); Lim, Kwon Taek, E-mail: ktlim@pknu.ac.kr [Department of Imaging System Engineering, Pukyong National University, Busan 608-737 (Korea, Republic of)

    2013-10-15

    A novel approach for the synthesis of poly(glycidyl methacrylate) grafted CdSe quantum dot (QDs) (PGMA-g-CdSe) was developed. The PGMA-g-CdSe nanohybrids were synthesized by the surface-initiated atom transfer radical polymerization of glycidyl methacrylate from the surface of the strategic initiator, CdSe-BrIB QDs prepared by the interaction of 2-bromoisobutyryl bromide (BrIB) and CdSe-OH QDs. The structure, morphology, and optical property of the PGMA-g-CdSe nanohybrids were analyzed by FT-IR, XPS, TGA, XRD, TEM, and PL. The as-synthesized PGMA-g-CdSe nanohybrids having multi-epoxide groups were employed for the direct coupling of biotin via ring-opening reaction of the epoxide groups to afford the Biotin-f-PGMA-g-CdSe nanobioconjugate. The covalent immobilization of biotin onto PGMA-g-CdSe was confirmed by FT-IR, XPS, and EDX. Biocompatibility and imaging properties of the Biotin-f-PGMA-g-CdSe were investigated by MTT bioassay and PL analysis, respectively. The cell viability study suggested that the biocompatibility was significantly enhanced by the functionalization of CdSe QDs by biotin and PGMA.

  2. Preparation of Mg(OH)_2 hybrid pigment by direct precipitation and graft onto cellulose fiber via surface-initiated atom transfer radical polymerization

    International Nuclear Information System (INIS)

    Wang, Xiao; Zhang, Yue; Lv, Lihua; Cui, Yongzhu; Wei, Chunyan; Pang, Guibing

    2016-01-01

    Graphical abstract: - Highlights: • Adsorbed anionic dye molecules are conducive to preferential growth of (0 0 1) plane of Mg(OH)_2 crystal for Mg(OH)_2 pigments. • Uniform coverage of nanosized Mg(OH)_2 pigments on fiber surface is achieved via surface-initiated ATRP. • About 4 wt% of Mg(OH)_2 pigment on fiber surface shortens nearly half of burning time of cellulose. - Abstract: Mg(OH)_2 flame retardant hybrid pigment is synthesized through simultaneous solution precipitation and adsorption of anionic dyes (C.I. Acid Red 6). The Mg(OH)_2 hybrid pigment bearing vinyl groups after surface silane modification is immobilized onto the surface of bromo end-functional cellulose fiber by atom transfer radical polymerization (ATRP). The morphology and structure of Mg(OH)_2 pigments and cellulose fibers grafted with modified pigments are characterized. The thermal properties, flammability and color fastness of cellulose fibers grafted with modified pigments are measured. The results reveal that anionic dye molecules are adsorbed onto Mg(OH)_2 crystals and affect the formation of lamella-like Mg(OH)_2 crystals. The cellulose fiber grafted with modified Mg(OH)_2 hybrid pigment absorbs about four times heat more than original cellulose fiber with about 4% immobilization ratio of pigment, which shortens nearly half of afterflame time and afterglow time.

  3. Surface-Initiated Atom Transfer Radical Polymerization of Magnetite Nanoparticles with Statistical Poly(tert-butyl acrylate-poly(poly(ethylene glycol methyl ether methacrylate Copolymers

    Directory of Open Access Journals (Sweden)

    Patcharin Kanhakeaw

    2015-01-01

    Full Text Available This work presented the surface modification of magnetite nanoparticle (MNP with poly[(t-butyl acrylate-stat-(poly(ethylene glycol methyl ether methacrylate] copolymers (P[(t-BA-stat-PEGMA] via a surface-initiated “grafting from” atom transfer radical polymerization (ATRP. Loading molar ratio of t-BA to PEGMA was systematically varied (100 : 0, 75 : 25, 50 : 50, and 25 : 75, resp. such that the degree of hydrophilicity of the copolymers, affecting the particle dispersibility in water, can be fine-tuned. The reaction progress in each step of the synthesis was monitored via Fourier transform infrared spectroscopy (FTIR. The studies in the reaction kinetics indicated that PEGMA had higher reactivity than that of t-BA in the copolymerizations. Gel permeation chromatography (GPC indicated that the molecular weights of the copolymers increased with the increase of the monomer conversion. Transmission electron microscopy (TEM revealed that the particles were spherical with averaged size of 8.1 nm in diameter. Dispersibility of the particles in water was apparently improved when the copolymers were coated as compared to P(t-BA homopolymer coating. The percentages of MNP and the copolymer in the composites were determined via thermogravimetric analysis (TGA and their magnetic properties were investigated via vibrating sample magnetometry (VSM.

  4. Ternary hybrid polymeric nanocomposites through grafting of polystyrene on graphene oxide-TiO{sub 2} by surface initiated atom transfer radical polymerization (SI-ATRP)

    Energy Technology Data Exchange (ETDEWEB)

    Kumar, Arvind; Bansal, Ankushi; Behera, Babita; Jain, Suman L.; Ray, Siddharth S., E-mail: ssray@iip.res.in

    2016-04-01

    A ternary hybrid of graphene oxide-titania-polystyrene (GO-TiO{sub 2}-PS) nanocomposite is developed where polystyrene composition is regulated by controlling growth of polymer chains and nanoarchitectonics is discussed. Graphene Oxide-TiO{sub 2} (GO-TiO{sub 2}) nanocomposite is prepared by in-situ hydrothermal method and the surface is anchored with α-bromoisobutyryl bromide to activate GO-TiO{sub 2} as initiator for polymerization. In-situ grafting of polystyrene through surface initiated atom transfer radical polymerization (SI- ATRP) on this Br-functionalized nano-composite initiator yields GO-TiO{sub 2}-PS ternary hybrid. Varying the monomer amount and keeping the concentration of initiator constant, polystyrene chain growth is regulated with narrow poly-dispersivity to achieve desired composition. This composite is well characterized by various analytical techniques like FTIR, XRD, DSC, SEM, TEM, and TGA. - Highlights: • Nanocomposite of ternary hybrid of GO-TiO{sub 2} with polystyrene. • PS is surface grafted on GO-TiO{sub 2}. • Polymer chain lengths are well regulated by SI-ATRP living polymerization. • Thermal stability of this hybrid is relatively high.

  5. Ternary hybrid polymeric nanocomposites through grafting of polystyrene on graphene oxide-TiO_2 by surface initiated atom transfer radical polymerization (SI-ATRP)

    International Nuclear Information System (INIS)

    Kumar, Arvind; Bansal, Ankushi; Behera, Babita; Jain, Suman L.; Ray, Siddharth S.

    2016-01-01

    A ternary hybrid of graphene oxide-titania-polystyrene (GO-TiO_2-PS) nanocomposite is developed where polystyrene composition is regulated by controlling growth of polymer chains and nanoarchitectonics is discussed. Graphene Oxide-TiO_2 (GO-TiO_2) nanocomposite is prepared by in-situ hydrothermal method and the surface is anchored with α-bromoisobutyryl bromide to activate GO-TiO_2 as initiator for polymerization. In-situ grafting of polystyrene through surface initiated atom transfer radical polymerization (SI- ATRP) on this Br-functionalized nano-composite initiator yields GO-TiO_2-PS ternary hybrid. Varying the monomer amount and keeping the concentration of initiator constant, polystyrene chain growth is regulated with narrow poly-dispersivity to achieve desired composition. This composite is well characterized by various analytical techniques like FTIR, XRD, DSC, SEM, TEM, and TGA. - Highlights: • Nanocomposite of ternary hybrid of GO-TiO_2 with polystyrene. • PS is surface grafted on GO-TiO_2. • Polymer chain lengths are well regulated by SI-ATRP living polymerization. • Thermal stability of this hybrid is relatively high.

  6. Synthesis and characterization of TiO2/Ag/polymer ternary nanoparticles via surface-initiated atom transfer radical polymerization

    International Nuclear Information System (INIS)

    Park, Jung Tae; Koh, Joo Hwan; Seo, Jin Ah; Cho, Yong Soo; Kim, Jong Hak

    2011-01-01

    We report on the novel ternary hybrid materials consisting of semiconductor (TiO 2 ), metal (Ag) and polymer (poly(oxyethylene methacrylate) (POEM)). First, a hydrophilic polymer, i.e. POEM, was grafted from TiO 2 nanoparticles via the surface-initiated atom transfer radical polymerization (ATRP) technique. These TiO 2 -POEM brush nanoparticles were used to template the formation of Ag nanoparticles by introduction of a AgCF 3 SO 3 precursor and a NaBH 4 aqueous solution for reduction process. Successful grafting of polymeric chains from the surface of TiO 2 nanoparticles and the in situ formation of Ag nanoparticles within the polymeric chains were confirmed using transmission electron microscopy (TEM), UV-vis spectroscopy, X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). FT-IR spectroscopy also revealed the specific interaction of Ag nanoparticles with the C=O groups of POEM brushes. This study presents a simple route for the in situ synthesis of both metal and polymer confined within the semiconductor, producing ternary hybrid inorganic-organic nanomaterials.

  7. Antibacterial inorganic-organic hybrid coatings on stainless steel via consecutive surface-initiated atom transfer radical polymerization for biocorrosion prevention.

    Science.gov (United States)

    Yuan, S J; Pehkonen, S O; Ting, Y P; Neoh, K G; Kang, E T

    2010-05-04

    To enhance the corrosion resistance of stainless steel (SS) and to impart its surface with antibacterial functionality for inhibiting biofilm formation and biocorrosion, well-defined inorganic-organic hybrid coatings, consisting of a polysilsesquioxane inner layer and quaternized poly(2-(dimethyamino)ethyl methacrylate) (P(DMAEMA)) outer blocks, were prepared via successive surface-initiated atom transfer radical polymerization (ATRP) of 3-(trimethoxysilyl)propyl methacrylate (TMSPMA) and 2-(dimethylamino)ethyl methacrylate (DMAEMA). The cross-linked P(TMASPMA), or polysilsesquioxane, inner layer provided a durable and resistant coating to electrolytes. The pendant tertiary amino groups of the P(DMAEMA) outer block were quaternized with alkyl halide to produce a high concentration of quaternary ammonium groups with biocidal functionality. The so-synthesized inorganic-organic hybrid coatings on the SS substrates exhibited good anticorrosion and antibacterial effects and inhibited biocorrosion induced by sulfate-reducing bacteria (SRB) in seawater media, as revealed by antibacterial assay and electrochemical analyses, and they are potentially useful to steel-based equipment under harsh industrial and marine environments.

  8. Grafting of antibacterial polymers on stainless steel via surface-initiated atom transfer radical polymerization for inhibiting biocorrosion by Desulfovibrio desulfuricans.

    Science.gov (United States)

    Yuan, S J; Xu, F J; Pehkonen, S O; Ting, Y P; Neoh, K G; Kang, E T

    2009-06-01

    To enhance the biocorrosion resistance of stainless steel (SS) and to impart its surface with bactericidal function for inhibiting bacterial adhesion and biofilm formation, well-defined functional polymer brushes were grafted via surface-initiated atom transfer radical polymerization (ATRP) from SS substrates. The trichlorosilane coupling agent, containing the alkyl halide ATRP initiator, was first immobilized on the hydroxylated SS (SS-OH) substrates for surface-initiated ATRP of (2-dimethylamino)ethyl methacrylate (DMAEMA). The tertiary amino groups of covalently immobilized DMAEMA polymer or P(DMAEMA), brushes on the SS substrates were quaternized with benzyl halide to produce the biocidal functionality. Alternatively, covalent coupling of viologen moieties to the tertiary amino groups of P(DMAEMA) brushes on the SS surface resulted in an increase in surface concentration of quaternary ammonium groups, accompanied by substantially enhanced antibacterial and anticorrosion capabilities against Desulfovibrio desulfuricans in anaerobic seawater, as revealed by antibacterial assay and electrochemical studies. With the inherent advantages of high corrosion resistance of SS, and the good antibacterial and anticorrosion capabilities of the viologen-quaternized P(DMAEMA) brushes, the functionalized SS is potentially useful in harsh seawater environments and for desalination plants. Copyright 2009 Wiley Periodicals, Inc.

  9. Poly(glycidyl methacrylate) grafted CdSe quantum dots by surface-initiated atom transfer radical polymerization: Novel synthesis, characterization, properties, and cytotoxicity studies

    International Nuclear Information System (INIS)

    Bach, Long Giang; Islam, Md. Rafiqul; Lee, Doh Chang; Lim, Kwon Taek

    2013-01-01

    A novel approach for the synthesis of poly(glycidyl methacrylate) grafted CdSe quantum dot (QDs) (PGMA-g-CdSe) was developed. The PGMA-g-CdSe nanohybrids were synthesized by the surface-initiated atom transfer radical polymerization of glycidyl methacrylate from the surface of the strategic initiator, CdSe-BrIB QDs prepared by the interaction of 2-bromoisobutyryl bromide (BrIB) and CdSe-OH QDs. The structure, morphology, and optical property of the PGMA-g-CdSe nanohybrids were analyzed by FT-IR, XPS, TGA, XRD, TEM, and PL. The as-synthesized PGMA-g-CdSe nanohybrids having multi-epoxide groups were employed for the direct coupling of biotin via ring-opening reaction of the epoxide groups to afford the Biotin-f-PGMA-g-CdSe nanobioconjugate. The covalent immobilization of biotin onto PGMA-g-CdSe was confirmed by FT-IR, XPS, and EDX. Biocompatibility and imaging properties of the Biotin-f-PGMA-g-CdSe were investigated by MTT bioassay and PL analysis, respectively. The cell viability study suggested that the biocompatibility was significantly enhanced by the functionalization of CdSe QDs by biotin and PGMA.

  10. Preparation of high-capacity, weak anion-exchange membranes by surface-initiated atom transfer radical polymerization of poly(glycidyl methacrylate) and subsequent derivatization with diethylamine

    International Nuclear Information System (INIS)

    Qian, Xiaolei; Fan, Hua; Wang, Chaozhan; Wei, Yinmao

    2013-01-01

    Ion-exchange membrane is of importance for the development of membrane chromatography. In this work, a high-capacity anion-exchange membrane was prepared by grafting of glycidyl methacrylate (GMA) onto the surface of regenerated cellulose (RC) membranes via surface-initiated atom transfer radical polymerization (SI-ATRP) and subsequent derivatization with diethylamine. Attenuated total reflectance Fourier-transform infrared (ATR-FTIR), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) were used to characterize changes in the chemical functionality, surface topography and pore morphology of the modified membranes. The static capacity of the prepared anion-exchange membrane was evaluated with bovine serum albumin (BSA) as a model protein. The results indicated that the anion-exchange membrane which could reach a maximum capacity of 96 mg/mL for static adsorption possesses a higher adsorption capacity, and the adsorption capacity increases with the polymerization time. The effect of pH and salt concentration confirmed that the adsorption of BSA followed ion-exchange mechanism. The established method would have potential application in the preparation of anion-exchange membrane.

  11. End-Functionalized Poly(N-isopropylacrylamide with d-Glucosamine through Different Initiator from C-1 and C-2 Positions via Atom Transfer Radical Polymerization

    Directory of Open Access Journals (Sweden)

    Guihua Cui

    2016-11-01

    Full Text Available Regioselective modification of d-glucosamine (2-amino-2-deoxy-d-glucopyranose, GA through C-1 and C-2 positions to synthesized thermo-responsive D-Glucosamine-poly(N-iso-propylacrylamide (PNIPAM via atom transfer radical polymerization (ATRP was investigated for the first time. Two different schemes of the synthesis for GA derivatives (GA-PNIPAM (i and (ii with well-defined structures using 3,4,6-tri-o-acetyl-2-deoxy-2-phthalimido-β-d-glucopyranose and 1,3,4,6-tetra-o-acetyl-2-amino-2-deoxy-β-d-glucopyranose intermediates were examined. The GA-PNIPAM (ii had an amino at C-2 position, while there was a hydroxyl in GA-PNIPAM (i at this position. Both the resulting oligomers (i and (ii had a narrow dispersity, and no significant cytotoxic response of copolymers (i and (ii was observed in the cell line over the concentration range from 0.1 μg/mL to 1000 μg/mL at any of the exposure times. In addition, it was discovered that GA-PNIPAM (i and (ii inhibited the proliferation of Human Hepatocellular Carcinoma Cells HepG2 as the concentration and the time changed, and the inhibitory activity of polymer (ii was higher than that of he (i. The results suggest that the GA-PNIPAM polymers show excellent biocompatibility in vitro.

  12. Cotton fibers encapsulated with homo- and block copolymers: synthesis by the atom transfer radical polymerization grafting-from technique and solid-state NMR dynamic investigations.

    Science.gov (United States)

    Castelvetro, Valter; Geppi, Marco; Giaiacopi, Simone; Mollica, Giulia

    2007-02-01

    Cotton fibers were modified by surface-initiated atom transfer radical polymerization of ethyl acrylate (EA) followed by copolymerization with styrene. Either ethyl 2-bromopropionate as a sacrificial free initiator or Cu(II) as a deactivator was used to optimize the EA grafting yield and to preserve the livingness of the chain ends for the subsequent growth of a poly(styrene) (PSty) block from the poly(ethyl acrylate) (PEA) grafts. The polymer-encapsulated cotton fibers were analyzed by Fourier transform infrared spectroscopy, scanning electron microscopy, differential scanning calorimetry (DSC), thermogravimetric analysis, and solid-state NMR (high-resolution 13C cross-polarization magic angle spinning, 1H spin-lattice relaxation times, and 1H free induction decay analysis NMR). The latter allowed the detection of the dynamic modifications associated with the presence of homo- and block copolymer grafts. In particular, the results of the DSC and NMR investigations suggest a heterogeneous morphology of the g-PEA-b-PSty grafted skin, which could be described as an inner layer of g-PEA sandwiched between the semicrystalline cellulose of the core fiber and the high glass transition temperature PSty of the covalently linked outer layer. Such morphology results in a reduced molecular mobility of the PEA chains.

  13. High time resolution measurements of the thermosphere from Fabry-Perot Interferometer measurements of atomic oxygen

    Directory of Open Access Journals (Sweden)

    E. A. K. Ford

    2007-06-01

    Full Text Available Recent advances in the performance of CCD detectors have enabled a high time resolution study of the high latitude upper thermosphere with Fabry-Perot Interferometers (FPIs to be performed. 10-s integration times were used during a campaign in April 2004 on an FPI located in northern Sweden in the auroral oval. The FPI is used to study the thermosphere by measuring the oxygen red line emission at 630.0 nm, which emits at an altitude of approximately 240 km. Previous time resolutions have been 4 min at best, due to the cycle of look directions normally observed. By using 10 s rather than 40 s integration times, and by limiting the number of full cycles in a night, high resolution measurements down to 15 s were achievable. This has allowed the maximum variability of the thermospheric winds and temperatures, and 630.0 nm emission intensities, at approximately 240 km, to be determined as a few minutes. This is a significantly greater variability than the often assumed value of 1 h or more. A Lomb-Scargle analysis of this data has shown evidence of gravity wave activity with waves with short periods. Gravity waves are an important feature of mesosphere-lower thermosphere (MLT dynamics, observed using many techniques and providing an important mechanism for energy transfer between atmospheric regions. At high latitudes gravity waves may be generated in-situ by localised auroral activity. Short period waves were detected in all four clear nights when this experiment was performed, in 630.0 nm intensities and thermospheric winds and temperatures. Waves with many periodicities were observed, from periods of several hours, down to 14 min. These waves were seen in all parameters over several nights, implying that this variability is a typical property of the thermosphere.

  14. Nonheme Fe(IV) Oxo Complexes of Two New Pentadentate Ligands and Their Hydrogen-Atom and Oxygen-Atom Transfer Reactions.

    Science.gov (United States)

    Mitra, Mainak; Nimir, Hassan; Demeshko, Serhiy; Bhat, Satish S; Malinkin, Sergey O; Haukka, Matti; Lloret-Fillol, Julio; Lisensky, George C; Meyer, Franc; Shteinman, Albert A; Browne, Wesley R; Hrovat, David A; Richmond, Michael G; Costas, Miquel; Nordlander, Ebbe

    2015-08-03

    Two new pentadentate {N5} donor ligands based on the N4Py (N4Py = N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)methylamine) framework have been synthesized, viz. [N-(1-methyl-2-benzimidazolyl)methyl-N-(2-pyridyl)methyl-N-(bis-2-pyridyl methyl)amine] (L(1)) and [N-bis(1-methyl-2-benzimidazolyl)methyl-N-(bis-2-pyridylmethyl)amine] (L(2)), where one or two pyridyl arms of N4Py have been replaced by corresponding (N-methyl)benzimidazolyl-containing arms. The complexes [Fe(II)(CH3CN)(L)](2+) (L = L(1) (1); L(2) (2)) were synthesized, and reaction of these ferrous complexes with iodosylbenzene led to the formation of the ferryl complexes [Fe(IV)(O)(L)](2+) (L = L(1) (3); L(2) (4)), which were characterized by UV-vis spectroscopy, high resolution mass spectrometry, and Mössbauer spectroscopy. Complexes 3 and 4 are relatively stable with half-lives at room temperature of 40 h (L = L(1)) and 2.5 h (L = L(2)). The redox potentials of 1 and 2, as well as the visible spectra of 3 and 4, indicate that the ligand field weakens as ligand pyridyl substituents are progressively substituted by (N-methyl)benzimidazolyl moieties. The reactivities of 3 and 4 in hydrogen-atom transfer (HAT) and oxygen-atom transfer (OAT) reactions show that both complexes exhibit enhanced reactivities when compared to the analogous N4Py complex ([Fe(IV)(O)(N4Py)](2+)), and that the normalized HAT rates increase by approximately 1 order of magnitude for each replacement of a pyridyl moiety; i.e., [Fe(IV)(O)(L(2))](2+) exhibits the highest rates. The second-order HAT rate constants can be directly related to the substrate C-H bond dissociation energies. Computational modeling of the HAT reactions indicates that the reaction proceeds via a high spin transition state.

  15. Absolute atomic oxygen and nitrogen densities in radio-frequency driven atmospheric pressure cold plasmas: Synchrotron vacuum ultra-violet high-resolution Fourier-transform absorption measurements

    International Nuclear Information System (INIS)

    Niemi, K.; O'Connell, D.; Gans, T.; Oliveira, N. de; Joyeux, D.; Nahon, L.; Booth, J. P.

    2013-01-01

    Reactive atomic species play a key role in emerging cold atmospheric pressure plasma applications, in particular, in plasma medicine. Absolute densities of atomic oxygen and atomic nitrogen were measured in a radio-frequency driven non-equilibrium plasma operated at atmospheric pressure using vacuum ultra-violet (VUV) absorption spectroscopy. The experiment was conducted on the DESIRS synchrotron beamline using a unique VUV Fourier-transform spectrometer. Measurements were carried out in plasmas operated in helium with air-like N 2 /O 2 (4:1) admixtures. A maximum in the O-atom concentration of (9.1 ± 0.7)×10 20 m −3 was found at admixtures of 0.35 vol. %, while the N-atom concentration exhibits a maximum of (5.7 ± 0.4)×10 19 m −3 at 0.1 vol. %

  16. A first-principles study of structure, orbital interactions and atomic oxygen and OH adsorption on Mo-, Sc- and Y-doped nickel bimetallic clusters

    International Nuclear Information System (INIS)

    Das, Nishith Kumar; Shoji, Tetsuo

    2013-01-01

    Highlights: •Mo-doped nickel clusters are energetically more stable than the Sc and Y-doped clusters (n ⩾ 10). •Mo atom exhibits center at the cluster rather than edge, while Sc and Y atom sit at the edge. •The metallic s, d orbitals are mainly dominated on the stability of nanoclusters. •The oxygen and OH adsorption energy of Mo-doped cluster are higher than those of other nanoclusters. •2p Orbitals are strongly bonds with Mo 4d, and a weakly interacts with Ni 3d, 4s and Mo 5s orbitals. -- Abstract: Density functional theory (DFT) has been used to study the stability, orbitals interactions and oxygen and hydroxyl chemisorption properties of Ni n M (1 ⩽ n ⩽ 12) clusters. A single atom doped-nickel clusters increase the stability, and icosahedral Ni 12 Mo cluster is the most stable structure. Molybdenum atom prefers to exhibit center at the cluster (n ⩾ 10) rather than edge, while Sc and Y atom remain at the edge. The Ni–Mo bond lengths are smaller than the Ni–Sc and Ni–Y. The pDOS results show that the d–d orbitals interactions are mainly dominating on the stability of clusters, while p orbitals have a small effect on the stability. The Mo-doped nanoclusters have the highest oxygen and OH chemisorption energy, and the most favorable adsorption site is on the top Mo site. The larger cluster distortion is found for the Sc- and Y-doped structures compared to other clusters. The oxygen 2p orbitals are strongly hybridizing with the Mo 4d orbitals (n < 9) and a little interaction between oxygen 2p and Ni 3d, 4s and Mo 5s orbitals. The Mo-doped clusters are significantly increased the chemisorption energies that might improve the passive film adherence of nanoalloys

  17. Intramolecular hydrogen bonding in malonaldehyde and its radical analogues.

    Science.gov (United States)

    Lin, Chen; Kumar, Manoj; Finney, Brian A; Francisco, Joseph S

    2017-09-28

    High level Brueckner doubles with triples correction method-based ab initio calculations have been used to investigate the nature of intramolecular hydrogen bonding and intramolecular hydrogen atom transfer in cis-malonaldehyde (MA) and its radical analogues. The radicals considered here are the ones that correspond to the homolytic cleavage of C-H bonds in cis-MA. The results suggest that cis-MA and its radical analogues, cis-MA RS , and cis-MA RA , both exist in planar geometry. The calculated intramolecular O-H⋯O=C bond in cis-MA is shorter than that in the radical analogues. The intramolecular hydrogen bond in cis-MA is stronger than in its radicals by at least 3.0 kcal/mol. The stability of a cis-malonaldehyde radical correlates with the extent of electron spin delocalization; cis-MA RA , in which the radical spin is more delocalized, is the most stable MA radical, whereas cis-MA RS , in which the radical spin is strongly localized, is the least stable radical. The natural bond orbital analysis indicates that the intramolecular hydrogen bonding (O⋯H⋯O) in cis-malonaldehyde radicals is stabilized by the interaction between the lone pair orbitals of donor oxygen and the σ * orbital of acceptor O-H bond (n → σ * OH ). The calculated barriers indicate that the intramolecular proton transfer in cis-MA involves 2.2 kcal/mol lower barrier than that in cis-MA RS .

  18. [Effects of seawater immersion on the inflammatory response and oxygen free radical injury of rats with superficial partial-thickness scald at early stage].

    Science.gov (United States)

    Yang, Y X; Wang, J H; Liu, L; Zou, Q; Zhang, Y; Bai, Z

    2017-06-20

    Objective: To study the effects of seawater immersion on the inflammatory response and oxygen free radical injury of rats with superficial-thickness scald at early stage. Methods: Seventy Wistar rats were divided into healthy control group (HC, n =7), pure scald group (PS, n =21), scald+ fresh water immersion group (SF, n =21), and scald+ seawater immersion group (SS, n =21) according to the random number table. Rats in group HC did not receive any treatment, while 5% total body surface area superficial partial-thickness scald was made on the back of rats in the latter three groups. Rats in group PS lived freely immediately post burn, while wounds on the back of rats in groups SF and SS were immersed into fresh water and seawater, respectively. Serum and full-thickness skin tissue in the center of wounds on the back of 7 rats in groups PS, SF, and SS at post immersion (injury) hour (PIH) 2, 4, and 6 were collected, respectively, while serum and full-thickness skin tissue at the same position of the 7 rats in group HC were collected at PIH 6 of rats in other groups. Morphology of skin tissue was observed with HE staining; tumor necrosis factor-alpha (TNF-α) content in serum and skin tissue was determined by enzyme-linked immunosorbent assay; superoxide dismutase (SOD) content in serum and skin tissue was determined by hydroxylamine method; malondialdehyde content in serum and skin tissue was determined by thiobarbituric acid method. Data were processed with analysis of variance of factorial design, one-way analysis of variance, Welch test, LSD test, and Tamhane test. Results: (1) Epidermal cells of skin tissue of rats in group HC arranged in order and continuously, and the dermis tissue and accessory structures were clear and complete. The skin layer and epidermis of wounds of rats in group PS had no significant change, but the edema of epidermis and dermis and infiltration of inflammatory cells enhanced over time at PIH 2, 4, and 6. The horny layer of epidermis of

  19. Mechanism of formation and spatial distribution of lead atoms in quartz tube atomizers

    Science.gov (United States)

    Johansson, M.; Baxter, D. C.; Ohlsson, K. E. A.; Frech, W.

    1997-05-01

    The cross-sectional and longitudinal spatial distributions of lead atoms in a quartz tube (QT) atomizers coupled to a gas chromatograph have been investigated. A uniform analyte atom distribution over the cross-section was found in a QT having an inner diameter (i.d.) of 7 mm, whereas a 10 mm i.d. QT showed an inhomogeneous distribution. These results accentuate the importance of using QTs with i.d.s below 10 mm to fulfil the prerequirement of the Beer—Lambert law to avoid bent calibration curves. The influence of the make up gas on the formation of lead atoms from alkyllead compounds has been studied, and carbon monoxide was found equally efficient in promoting free atom formation as hydrogen. This suggests that hydrogen radicals are not essential for mediating the atomization of alkyllead in QT atomizers at ˜ 1200 K. Furthermore, thermodynamic equilibrium calculations describing the investigated system were performed supporting the experimental results. Based on the presented data, a mechanism for free lead atom formation in continuously heated QT atomizers is proposed; thermal atomization occurs under thermodynamic equilibrium conditions in a reducing gas. The longitudinal atom distribution has been further investigated applying other make up gases, N 2 and He. These results show the effect of the influx of atmospheric oxygen on the free lead atom formation. Calculations of the partial pressure of oxygen in the atomizer gas phase assuming thermodynamic equilibrium have been undertaken using a convective-diffusional model.

  20. Effect of hydromorphone hydrochloride combined with ropivacaine for PCEA after orthopedic surgery on the synthesis of pain mediators, inflammatory mediator and oxygen free radicals

    Directory of Open Access Journals (Sweden)

    Liang-Ying Luo

    2017-08-01

    Full Text Available Objective: To explore the effect of hydromorphone hydrochloride combined with ropivacaine for PCEA after orthopedic surgery on the synthesis of pain mediators, inflammatory mediator and oxygen free radicals. Methods: A total of 120 patients with fracture who underwent operation in the hospital between July 2014 and December 2016 were collected and divided into control group and observation group according to the random number table method, 60 cases in each group. Control group received morphine hydrochloride combined with ropivacaine for analgesia, observation group received hydromorphone hydrochloride combined with ropivacaine for analgesia, and the postoperative analgesia lasted for 48 h. The differences in serum levels of pain mediators, inflammatory mediators and oxidative stress indexes were compared between the two groups. Results: Immediately after operation, the differences in serum levels of pain mediators, inflammatory mediators and oxidative stress indexes were not statistically significant between the two groups. 48 h after operation, serum PGE2, SP, β-EP, IL-6, MCP-1, HMGB-1 and MDA levels of both groups of patients were significantly lower than those immediately after operation while Cu-Zn SOD and GSH-Px levels were significantly higher than those immediately after operation, and serum PGE2, SP, β-EP, IL-6, MCP-1, HMGB-1 and MDA levels of observation group were significantly lower than those of control group while Cu-Zn SOD and GSH-Px levels were significantly higher than those of control group. Conclusion: Hydromorphone hydrochloride combined with ropivacaine for PCEA after orthopedic surgery is effective in alleviating pain and inhibiting systemic inflammatory response.

  1. [Effects of Electroacupuncture Intervention on Oxygen Free Radicals and Expression of Apoptosis-related Proteins in Rats with Ischemic Learning and Memory Disorder].

    Science.gov (United States)

    Hou, Zhi-tao; Sun, Zhong-ren; Liu, Song-tao; Xiong, Sheng-biao; Liu, Yi-tian; Han, Xiao-xia; Sun, Hong-fang; Han, Yu-sheng; Yin, Hong-na; Xu, Jin-qiao; Li, Dong-dong

    2015-12-01

    To observe the effect of electroacupuncture (EA) therapy on levels of oxygen free radicals (OFR) and hippocampal apoptosis-related protein expression in ischemic learning-memory disorder rats so as to investigate its mechanisms underlying improvement of ischemic learning-memory impairment. A total of 60 SD rats were randomly divided into sham operation (sham), model, medication, and EA groups, with 15 rats in each group. The learning-memory disorder model was made by occlusion of bilateral carotid arteries. EA (2- 3 Hz, 2 mA) was applied to "Zhi San Zhen" ["Shenting" (GV 24) and bilateral "Benshen" (GB 13)] for 30 min, once a day for 3 weeks. The rats of the medication group were treated by lavage of Aricept (0.03 mg . kg(-1) . d(-1)), once daily for 3 weeks. The rats' learning-memory ability was detected by Morris water maze tests and the state of hippocampal apoptosis cells was observed by light microscope after TUNEL staining and the expression of hippocampal Bcl-2, Bax and Caspase-3 proteins was detected by immunohistochemistry. Serum and hippocampal superoxide dismutase (SOD) and glutathione peroxidase (GSH-Px) activity and malondialdehyde (MDA) contents were detected by chemical colorimetric analysis. Compared with the sham group, the escape latencies (place-navigation) after modeling were evidently prolonged, and the times of target-platform crossing in 90 sec (spatial probe test) considerably reduced in the model group (Plearning-memory ability. After the treatment for 21 d, the increased escape latency and the reduced target-platform crossing time in both EA and medication groups were reversed in comparison with the model group (Pmemory ability, and the effect of the EA group was significantly superior to that of the medication group (Plearning-memory ability in ischemic learning-memory disorder rats which may be associated with its effects in reducing blood and hippocampal OFR contents and hippocampal cellular apoptosis.

  2. Radical chemistry of artemisinin

    Energy Technology Data Exchange (ETDEWEB)

    Denisov, Evgenii T; Solodova, S L; Denisova, Taisa G [Institute of Problems of Chemical Physics, Russian Academy of Sciences, Chernogolovka, Moscow Region (Russian Federation)

    2011-12-29

    The review summarizes physicochemical characteristics of the natural sesquiterpene peroxide artemisinin. The kinetic schemes of transformations of artemisinin radicals under anaerobic conditions are presented and analyzed. The sequence of radical reactions of artemisinin in the presence of oxygen is considered in detail. Special emphasis is given to the intramolecular chain oxidation resulting in the transformation of artemisinin into polyatomic hydroperoxide. The kinetic characteristics of elementary reaction steps involving alkyl, alkoxyl, and peroxyl radicals generated from artemisinin are discussed. The results of testing of artemisinin and its derivatives for the antimalarial activity and the scheme of the biochemical synthesis of artemisinin in nature are considered.

  3. Radical chemistry of artemisinin

    Science.gov (United States)

    Denisov, Evgenii T.; Solodova, S. L.; Denisova, Taisa G.

    2010-12-01

    The review summarizes physicochemical characteristics of the natural sesquiterpene peroxide artemisinin. The kinetic schemes of transformations of artemisinin radicals under anaerobic conditions are presented and analyzed. The sequence of radical reactions of artemisinin in the presence of oxygen is considered in detail. Special emphasis is given to the intramolecular chain oxidation resulting in the transformation of artemisinin into polyatomic hydroperoxide. The kinetic characteristics of elementary reaction steps involving alkyl, alkoxyl, and peroxyl radicals generated from artemisinin are discussed. The results of testing of artemisinin and its derivatives for the antimalarial activity and the scheme of the biochemical synthesis of artemisinin in nature are considered.

  4. Radical chemistry of artemisinin

    International Nuclear Information System (INIS)

    Denisov, Evgenii T; Solodova, S L; Denisova, Taisa G

    2010-01-01

    The review summarizes physicochemical characteristics of the natural sesquiterpene peroxide artemisinin. The kinetic schemes of transformations of artemisinin radicals under anaerobic conditions are presented and analyzed. The sequence of radical reactions of artemisinin in the presence of oxygen is considered in detail. Special emphasis is given to the intramolecular chain oxidation resulting in the transformation of artemisinin into polyatomic hydroperoxide. The kinetic characteristics of elementary reaction steps involving alkyl, alkoxyl, and peroxyl radicals generated from artemisinin are discussed. The results of testing of artemisinin and its derivatives for the antimalarial activity and the scheme of the biochemical synthesis of artemisinin in nature are considered.

  5. Radical chemistry of artemisinin

    Energy Technology Data Exchange (ETDEWEB)

    Denisov, Evgenii T; Solodova, S L; Denisova, Taisa G [Institute of Problems of Chemical Physics, Russian Academy of Sciences, Chernogolovka, Moscow Region (Russian Federation)

    2010-12-29

    The review summarizes physicochemical characteristics of the natural sesquiterpene peroxide artemisinin. The kinetic schemes of transformations of artemisinin radicals under anaerobic conditions are presented and analyzed. The sequence of radical reactions of artemisinin in the presence of oxygen is considered in detail. Special emphasis is given to the intramolecular chain oxidation resulting in the transformation of artemisinin into polyatomic hydroperoxide. The kinetic characteristics of elementary reaction steps involving alkyl, alkoxyl, and peroxyl radicals generated from artemisinin are discussed. The results of testing of artemisinin and its derivatives for the antimalarial activity and the scheme of the biochemical synthesis of artemisinin in nature are considered.

  6. Kinetics of the reaction of F atoms with O2 and UV spectrum of FO2 radicals in the gas phase at 295 K

    DEFF Research Database (Denmark)

    Ellermann, T.; Sehested, J.; Nielsen, O.J.

    1994-01-01

    The ultraviolet absorption spectrum of FO2 radicals and the kinetics of the reaction of F atoms with O2 have been studied in the gas phase at 295 K using pulse radiolysis combined with kinetic UV spectroscopy. At 230 nm, sigma(FO2) = (5.08 +/- 0.70) X 10(-18) cm2 molecule-1. The kinetics of the r......The ultraviolet absorption spectrum of FO2 radicals and the kinetics of the reaction of F atoms with O2 have been studied in the gas phase at 295 K using pulse radiolysis combined with kinetic UV spectroscopy. At 230 nm, sigma(FO2) = (5.08 +/- 0.70) X 10(-18) cm2 molecule-1. The kinetics...

  7. Flavonoids as scavengers of nitric oxide radical.

    NARCIS (Netherlands)

    van Acker, S.A.B.E.; Tromp, M.N.J.L.; Haenen, G.R.M.M.; van der Vijgh, W.J.F.; Bast, A.

    1995-01-01

    Flavonoids are a group of naturally occurring compounds used, e.g., in the treatment of vascular endothelial damage. They are known to be excellent scavengers of oxygen free radicals. Since the nitric oxide radical (

  8. Dramatic Influence of an Anionic Donor on the Oxygen-Atom Transfer Reactivity of a MnV–Oxo Complex

    Science.gov (United States)

    Neu, Heather M; Quesne, Matthew G; Yang, Tzuhsiung; Prokop-Prigge, Katharine A; Lancaster, Kyle M; Donohoe, James; DeBeer, Serena; de Visser, Sam P; Goldberg, David P

    2014-01-01

    Addition of an anionic donor to an MnV(O) porphyrinoid complex causes a dramatic increase in 2-electron oxygen-atom-transfer (OAT) chemistry. The 6-coordinate [MnV(O)(TBP8Cz)(CN)]− was generated from addition of Bu4N+CN− to the 5-coordinate MnV(O) precursor. The cyanide-ligated complex was characterized for the first time by Mn K-edge X-ray absorption spectroscopy (XAS) and gives Mn–O=1.53 Å, Mn–CN=2.21 Å. In combination with computational studies these distances were shown to correlate with a singlet ground state. Reaction of the CN− complex with thioethers results in OAT to give the corresponding sulfoxide and a 2e−-reduced MnIII(CN)− complex. Kinetic measurements reveal a dramatic rate enhancement for OAT of approximately 24 000-fold versus the same reaction for the parent 5-coordinate complex. An Eyring analysis gives ΔH≠=14 kcal mol−1, ΔS≠=−10 cal mol−1 K−1. Computational studies fully support the structures, spin states, and relative reactivity of the 5- and 6-coordinate MnV(O) complexes. PMID:25256417

  9. Influence of crystal defects on the chemical reactivity of recoil atoms in oxygen-containing chromium compounds

    International Nuclear Information System (INIS)

    Costea, T.

    1969-01-01

    The influence of crystal defects on the chemical reactivity of recoil atoms produced by the reaction 50 Cr (n,γ) 51 Cr in oxygen-containing chromium compounds has been studied. Three methods have been used to introduce the defects: doping (K 2 CrO 4 doped with BaCrO 4 ), irradiation by ionizing radiation (K 2 CrO 4 irradiated in the presence of Li 2 CO 3 ) and non-stoichiometry (the semi-conducting oxides of the CrO 3 -Cr 2 O 3 series). The thermal annealing kinetics of the irradiated samples have been determined, and the activation energy has been calculated. In all cases it has been observed that there is a decrease in the activation energy for thermal annealing in the presence of the defects. In order to explain the annealing process, an electronic mechanism has been proposed based on the interaction between the recoil species and the charge-carriers (holes or electrons). (author) [fr

  10. Oxygen vacancy defect engineering using atomic layer deposited HfAlOx in multi-layered gate stack

    Science.gov (United States)

    Bhuyian, M. N.; Sengupta, R.; Vurikiti, P.; Misra, D.

    2016-05-01

    This work evaluates the defects in high quality atomic layer deposited (ALD) HfAlOx with extremely low Al (estimated by the high temperature current voltage measurement shows that the charged oxygen vacancies, V+/V2+, are the primary source of defects in these dielectrics. When Al is added in HfO2, the V+ type defects with a defect activation energy of Ea ˜ 0.2 eV modify to V2+ type to Ea ˜ 0.1 eV with reference to the Si conduction band. When devices were stressed in the gate injection mode for 1000 s, more V+ type defects are generated and Ea reverts back to ˜0.2 eV. Since Al has a less number of valence electrons than do Hf, the change in the co-ordination number due to Al incorporation seems to contribute to the defect level modifications. Additionally, the stress induced leakage current behavior observed at 20 °C and at 125 °C demonstrates that the addition of Al in HfO2 contributed to suppressed trap generation process. This further supports the defect engineering model as reduced flat-band voltage shifts were observed at 20 °C and at 125 °C.

  11. Simultaneous Laser-induced Fluorescence of Nitric Oxide and Atomic Oxygen in the Hypersonic Materials Environment Test System Arcjet Facility

    Science.gov (United States)

    Johansen, Craig; Lincoln, Daniel; Bathel, Brett; Inman, Jennifer; Danehy, Paul

    2014-01-01

    Simultaneous nitric oxide (NO) and atomic oxygen (O) laser induced fluorescence (LIF) experiments were performed in the Hypersonic Materials Environmental Test System (HYMETS) facility at the NASA Langley Research Center. The data serves as an experimental database for validation for chemical and thermal nonequilibrium models used in hypersonic flows. Measurements were taken over a wide range of stagnation enthalpies (6.7 - 18.5 MJ/kg) using an Earth atmosphere simulant with a composition of 75% N2, 20% O2, and 5% Ar (by volume). These are the first simultaneous measurements of NO and O LIF to be reported in literature for the HYMETS facility. The maximum O LIF mean signal intensity was observed at a stagnation enthalpy of approximately 12 MJ/kg while the maximum NO LIF mean signal intensity was observed at a stagnation enthalpy of 6.7 MJ/kg. Experimental results were compared to simple fluorescence model that assumes equilibrium conditions in the plenum and frozen chemistry in the isentropic nozzle expansion (Mach 5). The equilibrium calculations were performed using CANTERA v2.1.1 with 16 species. The fluorescence model captured the correlation in mean O and NO LIF signal intensities over the entire range of stagnation enthalpies tested. Very weak correlations between single-shot O and NO LIF intensities were observed in the experiments at all of the stagnation enthalpy conditions.

  12. Determination of mercury in ash and soil samples by oxygen flask combustion method-Cold vapor atomic fluorescence spectrometry (CVAFS)

    International Nuclear Information System (INIS)

    Geng Wenhua; Nakajima, Tsunenori; Takanashi, Hirokazu; Ohki, Akira

    2008-01-01

    A simple method was developed for the determination of mercury (Hg) in coal fly ash (CFA), waste incineration ash (WIA), and soil by use of oxygen flask combustion (OFC) followed by cold vapor atomic fluorescence spectrometry (CVAFS). A KMnO 4 solution was used as an absorbent in the OFC method, and the sample containing a combustion agent and an ash or soil sample was combusted by the OFC method. By use of Hg-free graphite as the combustion agent, the determination of Hg in ash and soil was successfully carried out; the Hg-free graphite was prepared by use of a mild pyrolysis procedure at 500 deg. C. For six certified reference materials (three CFA samples and three soil samples), the values of Hg obtained by this method were in good agreement with the certified or reference values. In addition, real samples including nine CFAs collected from some coal-fired power plants, five WIAs collected from waste incineration plants, and two soils were analyzed by the present method, and the data were compared to those from microwave-acid digestion (MW-AD) method

  13. Free Br atom and free radical reactions in the radiolysis of 1,2 dibromoethane (DBE) in air free aqueous solutions

    International Nuclear Information System (INIS)

    Lal, Manohar

    1986-01-01

    G(Br - ) have been reported in the free radical degradation of 1,2 DBE in Ar - and N 2 O-saturated solutions. It is clear from the results that a small chain reaction occurs, t-butanol radical reacts with 1,2 DBE to give Br - . At pH 12.3, high (Br - ) are attributed to another chain reaction involving O - radical anion. Dose rate studies confirm the occurrence of chain reaction. (author). 5 refs

  14. Components of the Bond Energy in Polar Diatomic Molecules, Radicals, and Ions Formed by Group-1 and Group-2 Metal Atoms.

    Science.gov (United States)

    Yu, Haoyu; Truhlar, Donald G

    2015-07-14

    Although many transition metal complexes are known to have high multireference character, the multireference character of main-group closed-shell singlet diatomic molecules like BeF, CaO, and MgO has been less studied. However, many group-1 and group-2 diatomic molecules do have multireference character, and they provide informative systems for studying multireference character because they are simpler than transition metal compounds. The goal of the present work is to understand these multireference systems better so that, ultimately, we can apply what we learn to more complicated multireference systems and to the design of new exchange-correlation functionals for treating multireference systems more adequately. Fourteen main-group diatomic molecules and one triatomic molecule (including radicals, cations, and anions, as well as neutral closed-shell species) have been studied for this article. Eight of these molecules contain a group-1 element, and six contain a group-2 element. Seven of these molecules are multireference systems, and eight of them are single-reference systems. Fifty-three exchange-correlation functionals of 11 types [local spin-density approximation (LSDA), generalized gradient approximation (GGA), nonseparable gradient approximation (NGA), global-hybrid GGA, meta-GGA, meta-NGA, global-hybrid meta GGA, range-separated hybrid GGA, range-separated hybrid meta-GGA, range-separated hybrid meta-NGA, and DFT augmented with molecular mechanics damped dispersion (DFT-D)] and the Hartree-Fock method have been applied to calculate the bond distance, bond dissociation energy (BDE), and dipole moment of these molecules. All of the calculations are converged to a stable solution by allowing the symmetry of the Slater determinant to be broken. A reliable functional should not only predict an accurate BDE but also predict accurate components of the BDE, so each bond dissociation energy has been decomposed into ionization potential (IP) of the electropositive

  15. Preparation of polymer brushes grafted graphene oxide by atom transfer radical polymerization as a new support for trypsin immobilization and efficient proteome digestion.

    Science.gov (United States)

    Guo, Cong; Zhao, Xinyuan; Zhang, Wanjun; Bai, Haihong; Qin, Weijie; Song, Haifeng; Qian, Xiaohong

    2017-08-01

    Highly efficient protein digestion is one of the key issues in the "bottom-up" strategy-based proteomic studies. Compared with the time-consuming solution-based free protease digestion, immobilized protease digestion offers a promising alternative with obviously improved sample processing throughput. In this study, we proposed a new immobilized protease digestion strategy using two kinds of polymer-grafted graphene oxide (GO) conjugated trypsin. The polymer brush grafted GO was prepared using in situ polymer growth on initiator-functionalized GO using surface-initiated atom transfer radical polymerization (SI-ATRP) and characterized by AFM, TEM, TGA, and XPS. The polymer brush grafted GO supports three-dimensional trypsin immobilization, which not only increases the loading amount but also improves accessibility towards protein substrates. Both of the two types of immobilized trypsin provide 700 times shorter digestion time, while maintaining comparable protein/peptide identification scale compared with that of free trypsin digestion. More interestingly, combined application of the two types of immobilized trypsin with different surface-grafted polymers leads to at least 18.3/31.3% enhancement in protein/peptide identification compared with that obtained by digestion using a single type, indicating the potential of this digestion strategy for deeper proteome coverage using limited mass spectrometer machine hour. We expect these advantages may find valuable application in high throughput clinical proteomic studies, which often involve processing of a large number of samples. Graphical abstract Preparation of polymer brushes grafted and trypsin immobilized graphene oxide and its application in proteome digestion and mass spectrometry identification.

  16. Preparation and self-assembly behavior of polystyrene-block-poly (dimethylaminoethyl methacrylate amphiphilic block copolymer using atom transfer radical polymerization

    Directory of Open Access Journals (Sweden)

    2008-03-01

    Full Text Available Asymmetric and semi-symmetric amphiphilic diblock copolymers polystyrene-block-poly (dimethylaminoethyl methacrylate (PS-b-PDMAEMA with the same PS block length of 62 repeat units and quite short (3 repeat units or equivalent (47 repeat units length of PDMAEMA have been prepared simply by varying the ratio of the bromine-terminated macroinitiator polystyrene (PS-Br to DMAEMA using atom transfer radical polymerization (ATRP. The chemical structures and compositions of the PS-b-PDMAEMA block copolymers are studied by nuclear magnetic resonance (NMR spectroscopy, gel permeation chromatography (GPC, and elementary analysis (EA. The self-assembly behaviors of copolymers in N,N-dimethyl formamide (DMF with different pH and dioxane/water binary solvent mixture by direct dissolution method (DD, are studied by transmission electron microscopy (TEM, electron diffracting analysis (EDA, and energy-dispersive analysis of X-rays (EDAX techniques. Transmission electron microscopy results suggest that asymmetric block copolymer PS62-b-PDMAEMA3 (the numbers in the form of footnotes represent repeated units of each monomer in the copolymer can form spherical core-shell micelles, large compound reverse micelles (LCRMs, hexagonal/rhombic phases, reverse hexagonal/rhombic phases, vesicles, reverse vesicles and necklace-like reverse micelles, controlled by common or selective solvent and pH, while most of the aggregates of semi-symmetric PS62-b-PDMAEMA47 are simply spherical, such as spherical core-shell micelles and reverse spherical core-shell micelles, besides hexagonal/rhombic phases. All above structures are controlled by three components of the free energy of aggregation: core-chain stretching, interfacial energy and intercoronal chain interaction.

  17. Surface polyPEGylation of Eu3+ doped luminescent hydroxyapatite nanorods through the combination of ligand exchange and metal free surface initiated atom transfer radical polymerization

    Science.gov (United States)

    Zeng, Guangjian; Liu, Meiying; Heng, Chunning; Huang, Qiang; Mao, Liucheng; Huang, Hongye; Hui, Junfeng; Deng, Fengjie; Zhang, Xiaoyong; Wei, Yen

    2017-03-01

    The Eu3+ doped luminescent hydroxyapatite (HAp) nanorods with uniform size and morphology can be synthesized by hydrothermal route. However, these HAp nanorods are coated by hydrophobic oleylamine, which makes them difficult to be dispersed in aqueous solution and impede their biomedical applications. In this work, Eu3+ doped luminescent polymers functionalized HAp nanorods were prepared through the combination of ligand exchange reaction and metal free surface initiated atom transfer radical polymerization (ATRP) method. In this procedure, the amino group functionalized HAp nanorods were first prepared by ligand exchange reaction using adenosine monophosphate (AMP) as ligand. Then the Br-containing initiators (HAp-Br) were introduced onto the surface of HAp-AMP nanorods through the amidation reaction. Finally, polymers functionalized HAp nanorods were prepared by metal free ATRP method using poly(ethylene glycol) methacrylate (PEGMA) as monomer and 10-phenylphenothiazine (PTH) as organic photocatalyst. The properties of these obtained HAp nanocomposites (HAP-polyPEGMA nanorods) were characterized by means of transmission electron microscopy, Fourier transformed infrared spectroscopy, X-ray photoelectron spectroscopy and thermogravimetric analysis in detail. The cell imaging of these HAP-polyPEGMA nanorods was examined using laser scanning confocal microscope to evaluate their biomedical applications. We demonstrated for the first time that hydrophobic luminescent HAp nanorods can be functionalized with polyPEGMA through the combination of ligand exchange reaction and metal free surface initiated ATRP. As compared with the traditional ATRP, the metal free ATRP can overcome the toxic and fluorescence quenching effects of metal catalysts such as copper ions. More importantly, the strategy described in this work should also be utilized for fabrications of many other luminescent polymer nanocomposites due to its good monomer adoptability.

  18. Muon substituted free radicals

    International Nuclear Information System (INIS)

    Burkhard, P.; Fischer, H.; Roduner, E.; Strub, W.; Gygax, F.N.; Brinkman, G.A.; Louwrier, P.W.F.; McKenna, D.; Ramos, M.; Webster, B.C.

    1984-01-01

    Spin polarized energetic positive muons are injected as magnetic probes into unsaturated organic liquids. They are implemented via fast chemical processes ( -10 s) in various molecules. Of particular interest among these are muonium substituted free radicals. The technique allows determination of accurate rate coefficients for fast chemical reactions of radicals. Furthermore, radiochemical processes occuring in picoseconds after injection of the muon are studied. Of fundamental interest are also the structural and dynamical implications of substituting a proton by a muon, or in other terms, a hydrogen atom by a muonium atom. Selected examples for each of these three types of experiments are given. (Auth.)

  19. Study of apical oxygen atoms in a spin-ladder cuprate compound by X-ray absorption spectroscopy near the Cu K edge

    Energy Technology Data Exchange (ETDEWEB)

    Hatterer, C.J.; Eustache, B.; Collin, L.; Beuran, C.F.; Partiot, C.; Germain, P.; Xu, X.Z.; Lagues, M. [CNRS, Paris (France). Surfaces et Supraconducteurs; Michalowicz, A. [Laboratoire de Physique des Milieux Desordonnes, Universite Paris XII Val-de-Marne, 61 avenue du general de Gaulle, 94010, Creteil Cedex (France)]|[LURE, Universite Paris Sud, 91405, Orsay Cedex (France); Moscovici, J. [Laboratoire de Physique des Milieux Desordonnes, Universite Paris XII Val-de-Marne, 61 avenue du general de Gaulle, 94010, Creteil Cedex (France); Deville Cavellin, C. [CNRS, Paris (France). Surfaces et Supraconducteurs]|[Laboratoire d`Electronique, Universite Paris XII Val-de-Marne, 61 av. du general de Gaulle, 94010, Creteil Cedex (France); Traverse, A. [LURE, Universite Paris Sud, 91405, Orsay Cedex (France)

    1997-04-01

    The structure of high-T{sub c} superconducting cuprate compounds is based on CuO{sub 2} planes alternating with blocks that behave as charge reservoirs. The apical oxygen atoms which belong to these reservoirs are suspected to play a role in the mechanism of superconductivity. It thus seems necessary to measure the amount of apical oxygen atoms in various compounds, as a function of the superconducting properties. Polarisation dependent X-ray absorption spectroscopy (XAS) measurements were performed near the Cu K-edge on three types of phases. We collected information about the neighbourhood of the copper atom in the cuprate planes and in the direction perpendicular to these planes. Two of these phases have well known structures: Bi2212 in which copper atoms are on a pyramidal site and infinite layer phase, a square planar cuprate without apical oxygen. We used the obtained results as reference data to study a new copper-rich phase related to the spin-ladder series. (orig.)

  20. Study of the Dissociative Processes in O{sub 2} Discharges. Development of an Atomic Oxygen Beam Source; Etude de la dissociation de O{sub 2} dans les decharges d'oxygene. Application a la realisation de sources d'atomes

    Energy Technology Data Exchange (ETDEWEB)

    Pagnon, Daniel

    1992-09-24

    The first part of this work is devoted to the study of dissociative processes in an oxygen glow discharge at low pressure (0,1-5 Torr, 1-80 mA). The kinetics of oxygen atoms has been determined supported by the measurements of atomic concentrations by VUV absorption spectroscopy and actinometry. The reaction coefficients for dissociative excitation and direct excitation of oxygen atoms have been calculated using the cross sections of the literature and a previously calculated EEDF. It has been demonstrated that dissociative excitation is negligible in respect with direct excitation for dissociation rates smaller than 2,5 %. An upper limit of 20 % for dissociative rates is observed. This limit has been explained by the increase of the atomic recombination at the discharge wall with increasing wall temperature. Using all these results, we have designed and optimized a source of oxygen atoms which has then been adapted on a MBE device. The spatial distribution of the atomic density has been measured in molecular jet by laser induced fluorescence (LIF) and Resonant Multi-Photon Ionization (RMPI). A stimulated emission has been evidenced and the coefficient for this process evaluated. A model for the effusion of atoms has been developed from which the flow of atoms on the sample can be predicted. This source has already been used in industrial MBE devices for in-situ oxidation of copper films, superconductors, and substrates for VLSI high speed applications. The methodology of this work and the diagnostics developed can be applied to other kinds of discharges, of other molecular gases, to design sources of atoms for the treatment of large area samples. (author) [French] Ce travail debute par l'etude de la dissociation dans une decharge luminescente d'oxygene a basse pression (0,1-5 torr, 1-80 ma). La cinetique des atomes d'oxygene a ete etablie a partir de la mesure des concentrations atomiques par spectroscopie d'absorption vuv et par actinometrie. Les coefficients de

  1. Atomic-Level Co3O4 Layer Stabilized by Metallic Cobalt Nanoparticles: A Highly Active and Stable Electrocatalyst for Oxygen Reduction.

    Science.gov (United States)

    Liu, Min; Liu, Jingjun; Li, Zhilin; Wang, Feng

    2018-02-28

    Developing atomic-level transition oxides may be one of the most promising ways for providing ultrahigh electrocatalytic performance for oxygen reduction reaction (ORR), compared with their bulk counterparts. In this article, we developed a set of atomically thick Co 3 O 4 layers covered on Co nanoparticles through partial reduction of Co 3 O 4 nanoparticles using melamine as a reductive additive at an elevated temperature. Compared with the original Co 3 O 4 nanoparticles, the synthesized Co 3 O 4 with a thickness of 1.1 nm exhibits remarkably enhanced ORR activity and durability, which are even higher than those obtained by a commercial Pt/C in an alkaline environment. The superior activity can be attributed to the unique physical and chemical structures of the atomic-level oxide featuring the narrowed band gap and decreased work function, caused by the escaped lattice oxygen and the enriched coordination-unsaturated Co 2+ in this atomic layer. Besides, the outstanding durability of the catalyst can result from the chemically epitaxial deposition of the Co 3 O 4 on the cobalt surface. Therefore, the proposed synthetic strategy may offer a smart way to develop other atomic-level transition metals with high electrocatalytic activity and stability for energy conversion and storage devices.

  2. Radical transfer between proteins: role of tyrosine, tryptophan and protein peroxyl radicals

    International Nuclear Information System (INIS)

    Irwin, J.A.; Ostdal, H.; Davies, M.J.

    1998-01-01

    Reaction of the Fe(III) forms of the heme proteins myoglobin (Mb) and horseradish peroxidase (HRP) with H 2 O 2 gives rise to high-oxidation-state heme-derived species which can be described as a Fe(IV)-oxo porphyrin radical-cation ('Compound 1'). In the case of Mb, the Fe(IV)-oxo porphyrin radical-cation undergoes rapid electron transfer with the surrounding protein to give protein (globin)-derived radicals and an Fe(lV)-oxo species ('Compound 2'). The globin-derived radicals have been shown to be located at two (or more) sites: Tyr-103 or Trp-14, with the latter radical known to react with oxygen to give a Trp-derived peroxyl radical (Mb-Trp-OO*). With HRP, the Fe(lV)-oxo porphyrin radical-cation carries out two successive one-electron oxidation reactions at the exposed heme edge to give firstly 'Compound 2' [the Fe(lV)oxo species] and then the resting Fe(III) state of the enzyme. n this study we have investigated whether the Trp-14 peroxyl radical from Mb and the Compound 1 and 2 species from HRP (in the absence and presence of free Tyr) can oxidise amino acids, peptides and proteins. Such reactions constitute intermolecular protein-to-protein radical transfer reactions and hence protein chain-oxidation. We have also examined whether these oxidants react with antioxidants. Reaction of these heme-protein derived oxidants with amino acids, proteins and antioxidants has been carried out at room temperature for defined periods of time before freeze-quenching to 77K to halt reaction. The radical species present in the reaction system at the time of freezing were subsequently examined by EPR spectroscopy at 77K. Three free amino acids, Tyr, Trp and Cys (with Cys the least efficient) have been shown to react rapidly with Mb-Trp-OO*, as evidenced by the loss of the characteristic EPR features of Mb-Trp-OO* on inclusion of increasing concentrations of the amino acids. All other amino acids are much less reactive. Evidence has also been obtained for (inefficient) hydrogen

  3. Resistance to the ionizing radiation in cells of human melanoma. Role of the antioxidant enzymes and of the free radicals of the oxygen

    International Nuclear Information System (INIS)

    Medina, V.; Cricco, G.; Massari, N.; Nunez, M.; Martin, G.; Mohanad, N.; Gutierrez, A.; Bergoc, R.; Rivera, E.; Crescenti, E.; Croci, M.

    2006-01-01

    The malignant melanoma is a highly aggressive and potentially lethal type of skin cancer. Previously we have reported that the cellular human lines of melanoma WM35 and M15 are resistant to the ionizing radiation (IR). The histamine (HA) although it has a regulator effect of the cellular proliferation in these lines, it is not capable of to modify the response to the IR like it makes with other malignant cellular lines. To investigate the bases of the radioresistance of the melanoma lines we have studied in the WM35 the production of free radicals of oxygen (ROS), the activity of the antioxidant enzymes and their modifications by action of the IR and of the HA. In studies in vitro the cells were treated with HA 10 μM from 20 hs before being irradiated with a dose of 2 Gy (source 137 Cs, dose rate 7.7 Gy/min). The ROS levels, superoxide anion (O 2 - ) and hydrogen peroxide (H 2 O 2 ) its were measured by flow cytometry using fluorescent coloring and the activity of dismutase superoxide (SOD), Catalase (CAT) and Glutathion Peroxidase (GPx) its were determined by spectrophotometric techniques and the protein levels by Western blot. The results indicate that in the cells WM35 the HA increases the production of H 2 O 2 in 96% and it diminishes lightly (17%) the levels of O 2 - . On the contrary, the IR diminishes the levels of H 2 O-2 in 47% and it increases in 46% those of O 2 - . In the irradiated cells the HA power the decrease of H 2 O 2 produced by the IR. The variation of the enzymes activity is coincident with these changes in the levels of ROS: the treatment with HA increases the activity of SOD and it diminishes that of CAT in cells without irradiating; on the other hand, in the irradiated cells the HA it diminishes the SOD significantly. On the base of these results we can conclude that the levels of H 2 O 2 are directly related with the sensitivity of the cells WM35 to the IR. The HA is able to modulate the activity of the antioxidant enzymes and the levels

  4. Some aspects of radiation-induced free-radical chemistry of biologically important molecules

    International Nuclear Information System (INIS)

    Sonntag, C. von

    1992-01-01

    Biologically relevant material is usually associated with considerable amounts of water. When ionizing radiation interacts with such material one must consider two modes of energy deposition: the direct effect (ionizing radiation is absorbed by the biomolecules) and the indirect effect (ionizing radiation is absorbed by the surrounding water). In the direct effect, radical cations plus electrons, and excited states of the biomolecules are formed. In the indirect effect the water is decomposed resulting in the formation of the water radicals OH,H and e aq - . These reactive intermediates then interact with the biomolecules. When such systems are irradiated oxygen is often present. As a result of this, the radicals formed in the biomolecules by the various routes are converted into the corresponding peroxyl radicals. In certain cases, e.g. with the nucleobases of DNA, radical cations can be produced in dilute aqueous solutions by radiation-generated SO 4 - radicals, and the fate of these nucleobase radical cations studied by pulse radiolysis and product analysis. Attention will be drawn to the fact that frequently some of the reaction products of the radical cations with water are identical to those formed by OH radical attack, but that there are also marked differences. Similarly, protonation of radical anions (formed by the reaction of solvated electrons with the biomolecules) and the reaction of H-atoms with these molecules can lead to radical intermediates with considerably differing characteristics. Our present knowledge of the variety of reactions of the peroxyl radicals occurring in aqueous solutions will be briefly discussed, emphasizing the large variety of HO 2 /O 2 - elimination reactions and pointing to the reversibility of the oxygen addition (RO 2 →R + O 2 ) in some systems recently studied. (author)

  5. Penile rehabilitation after radical prostatectomy

    DEFF Research Database (Denmark)

    Fode, Mikkel; Ohl, Dana A; Ralph, David

    2013-01-01

    The pathophysiology of erectile dysfunction after radical prostatectomy (RP) is believed to include neuropraxia, which leads to temporarily reduced oxygenation and subsequent structural changes in penile tissue. This results in veno-occlusive dysfunction, therefore, penile rehabilitation programmes...

  6. Production of hydroxyl radicals from abiotic oxidation of pyrite by oxygen under circumneutral conditions in the presence of low-molecular-weight organic acids

    Science.gov (United States)

    Zhang, Peng; Yuan, Songhu

    2017-12-01

    Besides acidic environments, pyrite oxidation also occurs in circumneutral environments, such as well-buffered marine and estuarine sediments and salt marshes where low-molecular-weight organic acids (LMWOAs) (e.g., citrate and oxalate) prevail. However, the production of hydroxyl radicals (radOH) from pyrite oxidation by oxygen (O2) in these circumneutral environments is poorly understood. In this study, radOH production was measured during the abiotic oxidation of pyrite by O2 under circumneutral conditions. A pyrite suspension (50 g/L pyrite) that was buffered at pH 6-8 was exposed to air for oxygenation in the dark. Benzoate (20 mM) was added into the suspension to trap radOH. At pH 7, the cumulative radOH reached 7.5 μM within 420 min in the absence of LMWOAs, whereas it increased to 14.8, 12 and 11.2 μM in the presence of 1 mM ethylenediaminotetraacetate, citrate and oxalate, respectively. When the citrate concentration, which serves as a LMWOAs model, was increased from 0.5 to 5 mM, the cumulative radOH increased from 10.3 to 27.3 μM within 420 min at pH 7. With the decrease in pH from 8 to 6, the cumulative radOH increased from 2.1 to 23.3 μM in the absence of LMWOAs, but it increased from 8.8 to 134.9 μM in the presence of 3 mM citrate. The presence of LMWOAs enhanced the radOH production from pyrite oxidation under circumneutral conditions. In the absence of LMOWAs, radOH is produced mostly from the oxidation of adsorbed Fe(II) by O2. In the presence of citrate, radOH production is attributed mainly to the oxidation of Fe(II)-citrate- by O2 and secondarily to the oxidation of H2O on surface-sulfur defects. The acceleration of pyrite oxidation by Fe(III)-citrate increases radOH production. Fe(II)-citrate- is generated mainly from the complexation of adsorbed Fe(II) by citrate and the reduction of Fe(III)-citrate, and the generation is suppressed by the oxidation of adsorbed Fe(II). Fe(III)-citrate is generated predominantly from Fe

  7. One electron transfer redox potentials of free radicals. I. The oxygen-superoxide system. Progress report, September 1, 1975--July 1, 1976

    International Nuclear Information System (INIS)

    Ilan, Y.A.; Czapski, G.; Meisel, D.

    1976-01-01

    The method of determination of Redox potentials of radicals, using the pulse radiolysis technique, is outlined. The method is based on the determination of equilibria constants of electron transfer reactions between the radicals and appropriate acceptors. The limitations of this technique are discussed. The redox potentials of several quinones--semi-quinones are calculated, as well as the standard redox potential of the peroxy radical. E 0 /sub O 2 /O 2 /sup -/ = -0.33 V and the redox oxidation properties of the peroxy radical in various systems and pH are discussed. The value determined for the redox potentials of O 2 /O 2 - is higher by more than 0.2 volts than earlier estimates, which has important implications on the possible role of O 2 - in biological processes of O 2 fixation

  8. Magnetism, Spin Texture, and In-Gap States: Atomic Specialization at the Surface of Oxygen-Deficient SrTiO_{3}.

    Science.gov (United States)

    Altmeyer, Michaela; Jeschke, Harald O; Hijano-Cubelos, Oliver; Martins, Cyril; Lechermann, Frank; Koepernik, Klaus; Santander-Syro, Andrés F; Rozenberg, Marcelo J; Valentí, Roser; Gabay, Marc

    2016-04-15

    Motivated by recent spin- and angular-resolved photoemission (SARPES) measurements of the two-dimensional electronic states confined near the (001) surface of oxygen-deficient SrTiO_{3}, we explore their spin structure by means of ab initio density functional theory (DFT) calculations of slabs. Relativistic nonmagnetic DFT calculations display Rashba-like spin winding with a splitting of a few meV and when surface magnetism on the Ti ions is included, bands become spin-split with an energy difference ∼100  meV at the Γ point, consistent with SARPES findings. While magnetism tends to suppress the effects of the relativistic Rashba interaction, signatures of it are still clearly visible in terms of complex spin textures. Furthermore, we observe an atomic specialization phenomenon, namely, two types of electronic contributions: one is from Ti atoms neighboring the oxygen vacancies that acquire rather large magnetic moments and mostly create in-gap states; another comes from the partly polarized t_{2g} itinerant electrons of Ti atoms lying further away from the oxygen vacancy, which form the two-dimensional electron system and are responsible for the Rashba spin winding and the spin splitting at the Fermi surface.

  9. Surface polyPEGylation of Eu{sup 3+} doped luminescent hydroxyapatite nanorods through the combination of ligand exchange and metal free surface initiated atom transfer radical polymerization

    Energy Technology Data Exchange (ETDEWEB)

    Zeng, Guangjian; Liu, Meiying [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); Heng, Chunning [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); Shaanxi Key Laboratory of Degradable Biomedical Materials, Shaanxi R& D Center of Biomaterials and Fermentation Engineering, School of Chemical and Engineering, Northwest University, Xi’an 710069 (China); Huang, Qiang; Mao, Liucheng; Huang, Hongye [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); Hui, Junfeng [Shaanxi Key Laboratory of Degradable Biomedical Materials, Shaanxi R& D Center of Biomaterials and Fermentation Engineering, School of Chemical and Engineering, Northwest University, Xi’an 710069 (China); Deng, Fengjie, E-mail: fengjiedeng@aliyun.com [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); Zhang, Xiaoyong, E-mail: xiaoyongzhang1980@gmail.com [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); Wei, Yen, E-mail: weiyen@tsinghua.edu.cn [Department of Chemistry and The Tsinghua Center for Frontier Polymer Research, Tsinghua University, Beijing 100084 (China)

    2017-03-31

    Highlights: • Surface modification of HAp nanorods through the combination of ligand exchange reaction and metal free SI-ATRP. • HAp-polyPEGMA displayed high water dispersibility, good biocompatibility and biological imaging capability. • Metal free ATRP can overcome the toxic and fluorescence quenching effects of metal catalysts of conventional ATRP. - Abstract: The Eu{sup 3+} doped luminescent hydroxyapatite (HAp) nanorods with uniform size and morphology can be synthesized by hydrothermal route. However, these HAp nanorods are coated by hydrophobic oleylamine, which makes them difficult to be dispersed in aqueous solution and impede their biomedical applications. In this work, Eu{sup 3+} doped luminescent polymers functionalized HAp nanorods were prepared through the combination of ligand exchange reaction and metal free surface initiated atom transfer radical polymerization (ATRP) method. In this procedure, the amino group functionalized HAp nanorods were first prepared by ligand exchange reaction using adenosine monophosphate (AMP) as ligand. Then the Br-containing initiators (HAp-Br) were introduced onto the surface of HAp-AMP nanorods through the amidation reaction. Finally, polymers functionalized HAp nanorods were prepared by metal free ATRP method using poly(ethylene glycol) methacrylate (PEGMA) as monomer and 10-phenylphenothiazine (PTH) as organic photocatalyst. The properties of these obtained HAp nanocomposites (HAP-polyPEGMA nanorods) were characterized by means of transmission electron microscopy, Fourier transformed infrared spectroscopy, X-ray photoelectron spectroscopy and thermogravimetric analysis in detail. The cell imaging of these HAP-polyPEGMA nanorods was examined using laser scanning confocal microscope to evaluate their biomedical applications. We demonstrated for the first time that hydrophobic luminescent HAp nanorods can be functionalized with polyPEGMA through the combination of ligand exchange reaction and metal free surface

  10. Surface polyPEGylation of Eu"3"+ doped luminescent hydroxyapatite nanorods through the combination of ligand exchange and metal free surface initiated atom transfer radical polymerization

    International Nuclear Information System (INIS)

    Zeng, Guangjian; Liu, Meiying; Heng, Chunning; Huang, Qiang; Mao, Liucheng; Huang, Hongye; Hui, Junfeng; Deng, Fengjie; Zhang, Xiaoyong; Wei, Yen

    2017-01-01

    Highlights: • Surface modification of HAp nanorods through the combination of ligand exchange reaction and metal free SI-ATRP. • HAp-polyPEGMA displayed high water dispersibility, good biocompatibility and biological imaging capability. • Metal free ATRP can overcome the toxic and fluorescence quenching effects of metal catalysts of conventional ATRP. - Abstract: The Eu"3"+ doped luminescent hydroxyapatite (HAp) nanorods with uniform size and morphology can be synthesized by hydrothermal route. However, these HAp nanorods are coated by hydrophobic oleylamine, which makes them difficult to be dispersed in aqueous solution and impede their biomedical applications. In this work, Eu"3"+ doped luminescent polymers functionalized HAp nanorods were prepared through the combination of ligand exchange reaction and metal free surface initiated atom transfer radical polymerization (ATRP) method. In this procedure, the amino group functionalized HAp nanorods were first prepared by ligand exchange reaction using adenosine monophosphate (AMP) as ligand. Then the Br-containing initiators (HAp-Br) were introduced onto the surface of HAp-AMP nanorods through the amidation reaction. Finally, polymers functionalized HAp nanorods were prepared by metal free ATRP method using poly(ethylene glycol) methacrylate (PEGMA) as monomer and 10-phenylphenothiazine (PTH) as organic photocatalyst. The properties of these obtained HAp nanocomposites (HAP-polyPEGMA nanorods) were characterized by means of transmission electron microscopy, Fourier transformed infrared spectroscopy, X-ray photoelectron spectroscopy and thermogravimetric analysis in detail. The cell imaging of these HAP-polyPEGMA nanorods was examined using laser scanning confocal microscope to evaluate their biomedical applicatio